WO2022182171A1 - Organic light-emitting device - Google Patents

Abstract

The present invention provides an organic light-emitting device having improved driving voltage, efficiency, and lifespan.

Description

organic light emitting device

The present invention relates to an organic light emitting device having improved driving voltage, efficiency, and lifetime.

Cross-Citation with Related Application(s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2021-0024931 dated February 24, 2021, and all contents disclosed in the documents of the Korean patent applications are incorporated as a part of this specification.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

An organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. The organic layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons It lights up when it falls back to the ground state.

In the organic light emitting device as described above, the development of an organic light emitting device having improved driving voltage, efficiency, and lifespan is continuously required.

[Prior art literature]

[Patent Literature]

(Patent Document 0001) Korean Patent Publication No. 10-2000-0051826

The present invention relates to an organic light emitting device having improved driving voltage, efficiency, and lifetime.

The present invention provides the following organic light emitting device:

anode,

cathode, and

a light emitting layer between the anode and the cathode;

The light emitting layer comprises (i) a compound represented by the following Chemical Formula 1, and (ii) a compound represented by the following Chemical Formula 2 or Chemical Formula 3,

Organic light emitting device:

[Formula 1]

In Formula 1,

L is a single bond; Or a substituted or unsubstituted C _6-60 arylene,

X is N; or CH, provided that at least two or more of X are N;

R is hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising any one or more selected from the group consisting of N, O and S,

Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising any one or more selected from the group consisting of N, O and S,

[Formula 2]

[Formula 3]

In Formulas 2 and 3,

R' is a substituent represented by the following formula (4), or a substituted or unsubstituted C _6-60 aryl,

When R' is a substituent represented by the following formula (4), R' ₁ to R' ₆ are each independently hydrogen or deuterium;

When R' is not a substituent represented by the following formula (4), one of R' ₁ to R' ₆ is a substituent represented by the following formula (4), and the rest are each independently hydrogen or deuterium;

[Formula 4]

In Formula 4,

L' is a single bond, a substituted or unsubstituted C _6-60 arylene, or a substituted or unsubstituted C _2-60 heteroarylene comprising at least one selected from the group consisting of N, O and S; ,

L' ₁ and L' ₂ are each independently selected from the group consisting of a single bond, substituted or unsubstituted C _6-60 arylene, or substituted or unsubstituted N, O and S. is C _2-60 heteroarylene,

Ar' ₁ and Ar' ₂ are each independently, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _2- containing at least one selected from the group consisting of N, O and S ₆₀ heteroaryl.

The organic light emitting device described above has excellent driving voltage, efficiency, and lifetime.

FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , and a cathode 4 .

2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8, and a cathode 4 did it

Hereinafter, it will be described in more detail to help the understanding of the present invention.

In this specification,

or

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an aryl phosphine group; Or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more, or substituted or unsubstituted, two or more of the above-exemplified substituents are linked. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but it is preferably from 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, in the ester group, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably from 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. However, the present invention is not limited thereto.

In the present specification, the boron group specifically includes a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like, but is not limited thereto.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

etc. can be However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group including at least one of O, N, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably from 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, an acridyl group , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia and a jolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the above-described alkyl group. In the present specification, the description of the heterocyclic group described above for heteroaryl among heteroarylamines may be applied. In the present specification, the alkenyl group among the aralkenyl groups is the same as the examples of the above-described alkenyl groups. In the present specification, the description of the above-described aryl group may be applied except that arylene is a divalent group. In the present specification, the description of the above-described heterocyclic group may be applied, except that heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the above-described aryl group or cycloalkyl group may be applied, except that it is formed by combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.

Hereinafter, the present invention will be described in detail for each configuration.

positive and negative

The anode and cathode used in the present invention mean electrodes used in an organic light emitting device.

As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multi-layered material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

light emitting layer

The light emitting layer used in the present invention refers to a layer capable of emitting light in the visible ray region by combining holes and electrons transferred from the anode and the cathode. In general, the light emitting layer includes a host material and a dopant material, and in the present invention, (i) a compound represented by Formula 1 below, and (ii) a compound represented by Formula 2 or Formula 3 below as hosts.

In Formula 1, preferably, L is a single bond; phenylene; or naphthylene. More preferably, L is a single bond; 1,4-phenylene; 1,3-phenylene; 1,2-phenylene; or 1,4-naphthylene.

Preferably, all X are N.

Preferably, R is hydrogen, deuterium, phenyl, biphenylyl, terphenylyl, naphthyl, phenylnaphthyl, naphthylphenyl, phenanthrenyl, triphenylenyl, fluoranthenyl, dibenzofuranyl, benzonaph tofuranyl, dibenzothiophenyl, or benzonaphthothiophenyl.

Preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, naphthylphenyl, phenylnaphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl .

Representative examples of the compound represented by Formula 1 are as follows.

In addition, the present invention provides a method for preparing a compound represented by Formula 1, as shown in Scheme 1 below:

[Scheme 1]

In Scheme 1, definitions other than X are the same as defined above, and X is halogen, preferably bromo or chloro. Reaction Scheme 1 is a Suzuki coupling reaction, and is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

In Formulas 2 and 3, preferably, R' is a substituent represented by Formula 4, or substituted or unsubstituted C _6-12 aryl. More preferably, R' is a substituent represented by the above formula (4), or phenyl, biphenyl, or naphthyl.

Preferably, L' is a single bond, or substituted or unsubstituted C _6-12 arylene. More preferably, L' is a single bond, phenylene, biphenyldiyl, terphenyldiyl, naphthylene, or -(phenylene)-(naphthylene)-. More preferably, L' is a single bond, 1,4-phenylene, 4,4'-biphenyldiyl, or 2,6-naphthylene.

Preferably, L' ₁ and L' ₂ are each independently a single bond, or a substituted or unsubstituted C _6-12 arylene. Preferably, L' ₁ and L' ₂ are each independently a single bond, phenylene, or biphenyldiyl. More preferably, L' ₁ and L' ₂ are each independently a single bond, 1,4-phenylene, or 4,4'-biphenyldiyl.

Preferably, Ar' ₁ and Ar' ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, naphthylphenyl, phenylnaphthyl, phenanthrenyl, dimethylfluorenyl, diphenylfluorene nyl, dibenzofuranyl, dibenzothiophenyl, 9H-carbazol-9-yl, or 9-phenyl-9H-carbazolyl.

Preferably, one of R' ₁ to R' ₄ is a substituent represented by Formula 4, and the rest are each independently hydrogen or deuterium; R' ₅ and R' ₆ are each independently hydrogen or deuterium.

Preferably, R' ₁ to R' ₄ are each independently hydrogen or deuterium; One of R' ₅ and R' ₆ is a substituent represented by Formula 4, and the rest is hydrogen or deuterium. Here, preferably, Ar' ₁ and Ar' ₂ are each independently, terphenylyl, naphthyl, phenanthrenyl, dimethylfluorenyl, diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl, 9H-carbazol-9-yl, or 9-phenyl-9H-carbazolyl. Or, preferably, Ar′ ₁ is phenyl and Ar′ ₂ is phenyl, biphenyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, 9H-carbazole-9- yl, or 9-phenyl-9H-carbazolyl; or Ar′ ₁ is biphenylyl, Ar′ ₂ is terphenylyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, 9H-carbazol-9-yl, or 9-phenyl-9H-carbazolyl to be. Here, preferably, L′ ₁ and L′ ₂ are each independently a single bond, phenylene, or biphenyldiyl, more preferably, L′ ₁ and L′ ₂ are each independently a single bond, 1,4-phenylene, or 4,4'-biphenyldiyl.

Representative examples of the compound represented by Formula 2 or 3 are as follows.

In addition, the present invention provides a method for preparing a compound in which R' ₁ is Formula 4 in the compound represented by Formula 2, as shown in Scheme 2 below, and the remaining compounds represented by Formula 2 and compounds represented by Formula 3 can also be prepared in a similar way.

[Scheme 2]

In Scheme 2, definitions other than X' and Y' are the same as defined above, X' is halogen, preferably bromo, or chloro, Y' is hydrogen when L' is a single bond, When L is not a single bond, it is -B(OH) ₂ . Scheme 2 is an amine substitution reaction or Suzuki coupling reaction, and is preferably performed in the presence of a palladium catalyst and a base, and the reactor for each reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

Meanwhile, the dopant material is not particularly limited as long as it is a material used in an organic light emitting device. Examples include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group. As the styrylamine compound, a substituted or unsubstituted It is a compound in which at least one arylvinyl group is substituted in the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

hole transport layer

The organic light emitting diode according to the present invention may include a hole transport layer between the light emitting layer and the anode.

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. A material capable of transporting holes from the anode or hole injection layer to the light emitting layer as a hole transport material. This is suitable.

Specific examples of the hole transport material include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

hole injection layer

The organic light emitting diode according to the present invention may further include a hole injection layer between the anode and the hole transport layer, if necessary.

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferred. In addition, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.

Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.

electron transport layer

The organic light emitting diode according to the present invention may include an electron transport layer between the light emitting layer and the cathode.

The electron transport layer is a layer that receives electrons from the electron injection layer formed on the cathode or the cathode, transports electrons to the light emitting layer, and inhibits the transfer of holes in the light emitting layer. As an electron transport material, electrons are well injected from the cathode As a material that can receive and transfer to the light emitting layer, a material with high electron mobility is suitable.

Specific examples of the electron transport material include an Al complex of 8-hydroxyquinoline; complexes containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

electron injection layer

The organic light emitting diode according to the present invention may further include an electron injection layer between the electron transport layer and the cathode, if necessary.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer. It is preferable to use a compound which prevents migration to a layer and is excellent in the ability to form a thin film.

Specific examples of the material that can be used as the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preole nylidene methane, anthrone, and the like, derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

organic light emitting device

The structure of the organic light emitting device according to the present invention is illustrated in FIG. 1 . FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , and a cathode 4 . 2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8, and a cathode 4 did it

The organic light emitting device according to the present invention may be manufactured by sequentially stacking the above-described components. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. And, after forming each of the above-mentioned layers thereon, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing on a substrate from the cathode material to the anode material in the reverse order of the above-described configuration (WO 2003/012890). In addition, the light emitting layer may be formed by a solution coating method as well as a vacuum deposition method for the host and dopant. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

Meanwhile, the organic light emitting device according to the present invention may be a top emission type, a back emission type, or a double side emission type depending on the material used.

The manufacturing of the organic light emitting device will be described in detail in Examples below. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

[Production Example]

compound 1-1

Compound 1-A (15 g, 60.9 mmol) and compound Trz1 (19.3 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (16.8 g, 121.7 mmol) was dissolved in water (50 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.9 g of compound sub1-A-1. (Yield 71%, MS: [M+H] ⁺ = 484)

In a nitrogen atmosphere, compound sub1-A-1 (15 g, 31 mmol) and compound sub1 (6.1 g, 31 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (8.6 g, 62 mmol) was dissolved in water (26 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of Compound 1-1. (Yield 66%, MS: [M+H] ⁺ = 602)

compound 1-2

Compound 1-A (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.5 g of compound sub1-A-2. (Yield 74%, MS: [M+H] ⁺ = 434)

In a nitrogen atmosphere, compound sub1-A-2 (15 g, 34.6 mmol) and compound sub2 (9.4 g, 34.6 mmol) were added to THF (300 ml), stirred and refluxed. After that, potassium carbonate (9.6 g, 69.1 mmol) was dissolved in water (29 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound 1-2. (Yield 66%, MS: [M+H] ⁺ = 626)

compound 1-3

Compound 1-A (15 g, 60.9 mmol) and compound Trz3 (19.3 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.2 g of compound sub1-A-3. (yield 79%, MS: [M+H] ⁺ = 484)

Compound sub1-A-3 (15 g, 31 mmol) and compound sub3 (7.1 g, 31 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (8.6 g, 62 mmol) was dissolved in water (26 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 1-3. (Yield 66%, MS: [M+H] ⁺ = 632)

compound 1-4

Compound 1-A (15 g, 60.9 mmol) and compound Trz4 (27 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26 g of compound sub1-A-4. (Yield 70%, MS: [M+H] ⁺ = 610)

Compound sub1-A-4 (15 g, 24.6 mmol) and compound sub (5.6 g, 24.6 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (6.8 g, 49.2 mmol) was dissolved in water (20 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2 g of compound 1-4. (yield 60%, MS: [M+H] ⁺ = 758)

compound 1-5

Compound 1-B (15 g, 60.9 mmol) and compound Trz5 (24 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.2 g of compound sub1-B-1. (Yield 77%, MS: [M+H] ⁺ = 560)

Compound sub1-B-1 (15 g, 26.8 mmol) and compound sub5 (3.3 g, 26.8 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (7.4 g, 53.6 mmol) was dissolved in water (22 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 1-5. (yield 80%, MS: [M+H] ⁺ = 602)

compound 1-6

Compound 1-B (15 g, 60.9 mmol) and compound Trz3 (19.3 g, 60.9 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.2 g of compound sub1-B-2. (Yield 62%, MS: [M+H] ⁺ = 484)

Compound sub1-B-2 (15 g, 31 mmol) and compound sub6 (7.6 g, 31 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (8.6 g, 62 mmol) was dissolved in water (26 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.3 g of compound 1-6. (yield 76%, MS: [M+H] ⁺ = 650)

compound 1-7

Compound 1-B (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of compound sub1-B-3. (yield 79%, MS: [M+H] ⁺ = 434)

Compound sub1-B-3 (15 g, 34.6 mmol) and compound sub7 (8.6 g, 34.6 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (9.6 g, 69.1 mmol) was dissolved in water (29 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4 g of compound 1-7. (Yield 74%, MS: [M+H] ⁺ = 602)

compounds 1-8

Compound sub1-B-2 (15 g, 31 mmol) and compound sub8 (8.1 g, 31 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (8.6 g, 62 mmol) was dissolved in water (26 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.5 g of compound 1-8. (yield 75%, MS: [M+H] ⁺ = 666)

compounds 1-9

Compound 1-B (15 g, 60.9 mmol) and compound Trz6 (22.4 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.7 g of compound sub1-B-4. (Yield 73%, MS: [M+H] ⁺ = 534)

Compound sub1-B-4 (15 g, 28.1 mmol) and compound sub9 (6 g, 28.1 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (7.8 g, 56.2 mmol) was dissolved in water (23 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6 g of compound 1-9. (Yield 62%, MS: [M+H] ⁺ = 666)

compounds 1-10

Compound 1-B (15 g, 60.9 mmol) and compound Trz7 (28.6 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.6 g of compound sub1-B-5. (Yield 74%, MS: [M+H] ⁺ = 636)

Compound sub1-B-5 (15 g, 23.6 mmol) and compound sub5 (2.9 g, 23.6 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (6.5 g, 47.2 mmol) was dissolved in water (20 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4 g of compound 1-5. (Yield 65%, MS: [M+H] ⁺ = 678)

compound 1-11

Compound 1-B (15 g, 60.9 mmol) and compound Trz8 (21.8 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.1 g of compound sub1-B-6. (Yield 63%, MS: [M+H] ⁺ = 524)

Compound sub1-B-6 (15 g, 28.6 mmol) and compound sub10 (4.9 g, 28.6 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (7.9 g, 57.3 mmol) was dissolved in water (24 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of compound 1-11. (Yield 65%, MS: [M+H] ⁺ = 616)

compound 1-12

Compound 1-C (15 g, 60.9 mmol) and compound Trz3 (19.3 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.6 g of compound sub1-C-1. (Yield 60%, MS: [M+H] ⁺ = 484)

Compound sub1-C-1 (15 g, 31 mmol) and compound sub10 (5.3 g, 31 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (8.6 g, 62 mmol) was dissolved in water (26 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 1-12. (Yield 72%, MS: [M+H] ⁺ = 576)

compound 1-13

Compound 1-C (15 g, 60.9 mmol) and compound Trz9 (24 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.5 g of compound sub1-C-2. (yield 69%, MS: [M+H] ⁺ = 560

Compound sub1-C-2 (15 g, 26.8 mmol) and compound sub10 (4.6 g, 26.8 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (7.4 g, 53.6 mmol) was dissolved in water (22 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of compound 1-13. (yield 80%, MS: [M+H] ⁺ = 652)

compound 1-14

Compound 1-C (15 g, 60.9 mmol) and compound Trz10 (20.9 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.5 g of compound sub1-C-3. (Yield 66%, MS: [M+H] ⁺ = 510)

Compound sub1-C-3 (15 g, 29.4 mmol) and compound sub11 (7.3 g, 29.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (8.1 g, 58.8 mmol) was dissolved in water (24 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.3 g of compound 1-14. (Yield 77%, MS: [M+H] ⁺ = 678)

compound 1-15

Compound 1-C (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.7 g of compound sub1-C-4. (Yield 71%, MS: [M+H] ⁺ = 434)

Compound sub1-C-4 (15 g, 37.1 mmol) and compound sub12 (9.7 g, 37.1 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (10.3 g, 74.3 mmol) was dissolved in water (31 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of compound 1-15. (Yield 64%, MS: [M+H] ⁺ = 616)

compound 1-16

Compound sub1-C-3 (15 g, 26.8 mmol) and compound sub13 (7.4 g, 26.8 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (7.4 g, 53.6 mmol) was dissolved in water (22 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.2 g of compound 1-16. (yield 80%, MS: [M+H] ⁺ = 758)

compound 1-17

Compound sub1-C-4 (15 g, 34.6 mmol) and compound sub14 (7.7 g, 34.6 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (9.6 g, 69.1 mmol) was dissolved in water (29 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound 1-17. (Yield 62%, MS: [M+H] ⁺ = 576)

compound 1-18

Compound sub1-C-1 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (8.6 g, 62 mmol) was dissolved in water (26 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12 g of compound 1-18. (Yield 63%, MS: [M+H] ⁺ = 616)

compound 1-19

Compound 1-C (15 g, 60.9 mmol) and compound Trz11 (22.4 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.4 g of compound sub1-C-5. (yield 69%, MS: [M+H] ⁺ = 534)

Compound sub1-C-5 (15 g, 28.1 mmol) and compound sub15 (6 g, 28.1 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (7.8 g, 56.2 mmol) was dissolved in water (23 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound 1-19. (Yield 71%, MS: [M+H] ⁺ = 666)

compound 1-20

Compound 1-C (15 g, 60.9 mmol) and compound Trz12 (21.8 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21 g of compound sub1-C-6. (Yield 66%, MS: [M+H] ⁺ = 524)

Compound sub1-C-6 (15 g, 28.6 mmol) and compound sub10 (4.9 g, 28.6 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in water (36 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound 1-20. (Yield 70%, MS: [M+H] ⁺ = 616)

compound 1-21

Compound 1-C (15 g, 60.9 mmol) and compound Trz13 (24 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.2 g of compound sub1-C-7. (Yield 77%, MS: [M+H] ⁺ = 560)

Compound sub1-C-7 (15 g, 26.8 mmol) and compound sub5 (3.3 g, 26.8 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in water (33 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5 g of compound 1-21. (Yield 65%, MS: [M+H] ⁺ = 602)

compound 1-22

Compound 1-D (15 g, 60.9 mmol) and compound Trz14 (19.3 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.9 g of compound sub1-D-1. (Yield 67%, MS: [M+H] ⁺ = 586)

In a nitrogen atmosphere, compound sub1-D-1 (15 g, 25.6 mmol) and compound sub5 (3.1 g, 25.6 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (10.6 g, 76.8 mmol) was dissolved in water (32 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.3 g of compound 1-22. (Yield 64%, MS: [M+H] ⁺ = 628)

compound 1-23

Compound 1-D (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20 g of compound sub1-D-2. (yield 76%, MS: [M+H] ⁺ = 434)

Compound sub1-D-2 (15 g, 34.6 mmol) and compound sub16 (9.1 g, 34.6 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in water (43 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of compound 1-23. (Yield 66%, MS: [M+H] ⁺ = 616)

compound 1-24

Compound 1-D (15 g, 60.9 mmol) and compound Trz10 (20.9 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of compound sub1-D-3. (Yield 67%, MS: [M+H] ⁺ = 510)

In a nitrogen atmosphere, compound sub1-D-3 (15 g, 29.4 mmol) and compound sub17 (7.7 g, 29.4 mmol) were added to THF (300 ml), stirred and refluxed. After that, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in water (37 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of compound 1-24. (Yield 61%, MS: [M+H] ⁺ = 692)

compound 1-25

Compound 1-D (15 g, 60.9 mmol) and compound Trz15 (21.8 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.3 g of compound sub1-D-4. (Yield 67%, MS: [M+H] ⁺ = 524)

Compound sub1-D-4 (15 g, 28.6 mmol) and compound sub10 (4.9 g, 28.6 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in water (36 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.7 g of compound 1-25. (Yield 61%, MS: [M+H] ⁺ = 616)

compound 1-26

Compound sub1-D-3 (15 g, 29.4 mmol) and compound sub18 (6.2 g, 29.4 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in water (37 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound 1-26. (yield 76%, MS: [M+H] ⁺ = 642)

compound 1-27

Compound 1-D (15 g, 60.9 mmol) and compound Trz16 (27 g, 60.9 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.1 g of compound sub1-D-5. (Yield 73%, MS: [M+H] ⁺ = 610)

Compound sub1-D-5 (15 g, 24.6 mmol) and compound sub9 (5.2 g, 24.6 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in water (31 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 1-27. (Yield 70%, MS: [M+H] ⁺ = 742)

compound 1-28

Compound 1-D (15 g, 60.9 mmol) and compound Trz13 (24 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of compound sub1-D-6. (Yield 61%, MS: [M+H] ⁺ = 560)

In a nitrogen atmosphere, compound sub1-D-6 (15 g, 26.8 mmol) and compound sub10 (4.6 g, 26.8 mmol) were added to THF (300 ml), stirred and refluxed. After that, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in water (33 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-28. (Yield 70%, MS: [M+H] ⁺ = 652)

compound 1-29

Compound 1-E (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.1 g of compound sub1-E-1. (Yield 65%, MS: [M+H] ⁺ = 434)

Compound sub1-E-1 (15 g, 34.6 mmol) and compound sub2 (9.4 g, 34.6 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in water (43 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.5 g of compound 1-29. (Yield 67%, MS: [M+H] ⁺ = 626)

compounds 1-30

Compound 1-E (15 g, 60.9 mmol) and compound Trz9 (24 g, 60.9 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.9 g of compound sub1-E-2. (yield 79%, MS: [M+H] ⁺ = 560)

Compound sub1-E-2 (15 g, 26.8 mmol) and compound sub19 (7 g, 26.8 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in water (33 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.9 g of Compound 1-30. (yield 80%, MS: [M+H] ⁺ = 742)

compound 1-31

Compound 1-E (15 g, 60.9 mmol) and compound Trz17 (22.4 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.3 g of compound sub1-E-3. (Yield 78%, MS: [M+H] ⁺ = 534)

Compound sub1-E-3 (15 g, 28.1 mmol) and compound sub2- (7.8 g, 28.1 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.6 g, 84.3 mmol) was dissolved in water (35 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.8 g of compound 1-31. (Yield 72%, MS: [M+H] ⁺ = 732)

compound 1-32

Compound sub1-E-1 (15 g, 34.6 mmol) and compound sub21 (7.7 g, 34.6 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in water (43 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 1-32. (Yield 65%, MS: [M+H] ⁺ = 576)

compound 1-33

Compound 1-E (15 g, 60.9 mmol) and compound Trz15 (21.8 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.5 g of compound sub1-E-4. (yield 80%, MS: [M+H] ⁺ = 524)

Compound sub1-E-4 (15 g, 28.6 mmol) and compound sub10 (4.9 g, 28.6 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in water (36 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6 g of compound 1-33. (yield 60%, MS: [M+H] ⁺ = 616)

compound 1-34

Compound 1-E (15 g, 60.9 mmol) and compound Trz3 (19.3 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.6 g of compound sub1-E-5. (Yield 60%, MS: [M+H] ⁺ = 484)

In a nitrogen atmosphere, compound sub1-E-5 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in water (39 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of compound 1-34. (yield 60%, MS: [M+H] ⁺ = 616)

compound 1-35

Compound 1-E (15 g, 60.9 mmol) and compound Trz10 (20.9 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.7 g of compound sub1-E-6. (Yield 70%, MS: [M+H] ⁺ = 510)

In a nitrogen atmosphere, compound sub1-E-6 (15 g, 29.4 mmol) and compound sub22 (7.7 g, 29.4 mmol) were added to THF (300 ml), stirred and refluxed. After that, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in water (37 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of compound 1-35. (Yield 72%, MS: [M+H] ⁺ = 692)

compound 1-36

Compound sub1-E-5 (15 g, 31 mmol) and compound sub23 (8.1 g, 31 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in water (39 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of compound 1-36. (Yield 60%, MS: [M+H] ⁺ = 666)

compound 1-37

Compound sub1-E-5 (15 g, 31 mmol) and compound sub10 (5.3 g, 31 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in water (39 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1 g of compound 1-37. (yield 79%, MS: [M+H] ⁺ = 576)

compound 1-38

Compound 1-E (15 g, 60.9 mmol) and compound Trz18 (27 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.1 g of compound sub1-E-7. (Yield 65%, MS: [M+H] ⁺ = 610)

Compound sub1-E-7 (15 g, 24.6 mmol) and compound sub5 (3 g, 24.6 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in water (31 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1 g of compound 1-38. (Yield 63%, MS: [M+H] ⁺ = 652)

compound 1-39

Compound 1-E (15 g, 60.9 mmol) and compound Trz13 (24 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.2 g of compound sub1-E-8. (Yield 77%, MS: [M+H] ⁺ = 560)

Compound sub1-E-8 (15 g, 26.8 mmol) and compound sub5 (3.3 g, 26.8 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in water (33 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9 g of compound 1-39. (Yield 68%, MS: [M+H] ⁺ = 602)

compound 1-40

Compound 1-F (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.2 g of compound sub1-F-1. (Yield 73%, MS: [M+H] ⁺ = 434)

In a nitrogen atmosphere, compound 1-F (15 g, 34.6 mmol) and compound sub6 (8.5 g, 34.6 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in water (43 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7 g of compound 1-40. (Yield 71%, MS: [M+H] ⁺ = 600)

compound 1-41

Compound 1-F (15 g, 60.9 mmol) and compound Trz10 (20.9 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.1 g of compound sub1-F-2. (Yield 68%, MS: [M+H] ⁺ = 510)

Compound sub1-F-2 (15 g, 29.4 mmol) and compound sub1 (5.8 g, 29.4 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, stirred and refluxed. After that, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in water (37 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of compound 1-41. (Yield 77%, MS: [M+H] ⁺ = 628)

compound 1-42

Compound Trz7 (15 g, 31.9 mmol) and compound sub9 (6.8 g, 31.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (13.2 g, 95.8 mmol) was dissolved in water (40 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2 g of compound 1-42. (yield 79%, MS: [M+H] ⁺ = 602)

compound 1-43

Compound Trz16 (15 g, 33.8 mmol) and compound sub9 (7.2 g, 33.8 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (14 g, 101.4 mmol) was dissolved in water (42 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound 1-43. (Yield 77%, MS: [M+H] ⁺ = 576)

compound 1-44

Compound Trz4 (15 g, 33.8 mmol) and compound sub9 (7.2 g, 33.8 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (14 g, 101.4 mmol) was dissolved in water (42 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of compound 1-44. (Yield 73%, MS: [M+H] ⁺ = 576)

compound 1-45

In a nitrogen atmosphere, compound Trz1 (15 g, 35.7 mmol) and compound sub9 (7.6 g, 35.7 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in water (44 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-45. (Yield 62%, MS: [M+H] ⁺ = 552)

compound 1-46

Compound Trz19 (15 g, 33.8 mmol) and compound sub9 (7.2 g, 33.8 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (14 g, 101.4 mmol) was dissolved in water (42 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of compound 1-46. (Yield 70%, MS: [M+H] ⁺ = 576)

compound 1-47

Compound Trz20 (15 g, 35.9 mmol) and compound sub9 (7.6 g, 35.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in water (45 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound 1-47. (yield 76%, MS: [M+H] ⁺ = 550)

compound 1-48

Compound Trz3 (15 g, 47.2 mmol) and compound sub24 (9.7 g, 47.2 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (19.6 g, 141.6 mmol) was dissolved in water (59 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of compound sub1-G-1. (Yield 62%, MS: [M+H] ⁺ = 444)

Compound sub1-G-1 (15 g, 33.8 mmol) and compound sub9 (7.2 g, 33.8 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (14 g, 101.4 mmol) was dissolved in water (42 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2 g of compound 1-48. (Yield 78%, MS: [M+H] ⁺ = 576)

compound 1-49

In a nitrogen atmosphere, 0 (15 g, 41.9 mmol) and compound sub25 (8.7 g, 41.9 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in water (52 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6 g of compound sub1-G-2. (Yield 62%, MS: [M+H] ⁺ = 484)

Compound sub1-G-2 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in water (39 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of compound 1-49. (Yield 72%, MS: [M+H] ⁺ = 616)

compounds 1-50

Compound Trz21 (15 g, 36.8 mmol) and compound sub26 (5.8 g, 36.8 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in water (46 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound sub1-G-3. (Yield 72%, MS: [M+H] ⁺ = 484)

Compound sub1-G-3 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in water (39 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of Compound 1-50. (yield 69%, MS: [M+H] ⁺ = 616)

compound 1-51

Compound Trz16 (15 g, 33.8 mmol) and compound sub27 (5.3 g, 33.8 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (14 g, 101.4 mmol) was dissolved in water (42 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound sub1-G-4. (yield 76%, MS: [M+H] ⁺ = 520)

Compound sub1-G-4 (15 g, 28.8 mmol) and compound sub9 (6.1 g, 28.8 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (12 g, 86.5 mmol) was dissolved in water (36 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound 1-51. (Yield 71%, MS: [M+H] ⁺ = 652)

compound 1-52

Compound Trz22 (15 g, 36.8 mmol) and compound sub28 (5.8 g, 36.8 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in water (46 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound sub1-G-5. (Yield 72%, MS: [M+H] ⁺ = 484)

Compound sub1-G-5 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in water (39 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of compound 1-52. (Yield 68%, MS: [M+H] ⁺ = 616)

compound 1-53

Compound Trz23 (15 g, 34.6 mmol) and compound sub27 (5.4 g, 34.6 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in water (43 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3 g of compound sub1-G-6. (Yield 64%, MS: [M+H] ⁺ = 510)

Compound sub1-G-5 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in water (39 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of compound 1-53. (Yield 68%, MS: [M+H] ⁺ = 616)

compound 1-54

In a nitrogen atmosphere, compound sub1-G-1 (15 g, 33.8 mmol) and compound 1-E (8.3 g, 33.8 mmol) were added to THF (300 ml), stirred and refluxed. After that, potassium carbonate (14 g, 101.4 mmol) was dissolved in water (42 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.4 g of compound sub1-E-9. (Yield 70%, MS: [M+H] ⁺ = 610)

Compound sub1-E-9 (15 g, 24.6 mmol) and compound sub5 (3 g, 24.6 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in water (31 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-54. (yield 76%, MS: [M+H] ⁺ = 652)

compound 1-55

In a nitrogen atmosphere, 0 (15 g, 56 mmol) and compound sub24 (11.6 g, 56 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (23.2 g, 168.1 mmol) was dissolved in water (70 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.6 g of compound sub1-G-7. (Yield 71%, MS: [M+H] ⁺ = 394)

Compound sub1-G-7 (15 g, 38.1 mmol) and compound 1-E (9.4 g, 38.1 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in water (47 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound sub1-B-7. (Yield 65%, MS: [M+H] ⁺ = 560)

Compound sub1-B-7 (15 g, 26.8 mmol) and compound sub5 (3.3 g, 26.8 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in water (33 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 1-55. (yield 80%, MS: [M+H] ⁺ = 602)

compound 1-56

In a nitrogen atmosphere, compound sub1-G-7 (15 g, 38.1 mmol) and compound 1-E (9.4 g, 38.1 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in water (47 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound sub1-B-7. (Yield 65%, MS: [M+H] ⁺ = 560)

Compound sub1-G-8 (15 g, 30 mmol) and compound sub9 (6.4 g, 30 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (12.4 g, 90 mmol) was dissolved in water (37 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of compound 1-56. (Yield 71%, MS: [M+H] ⁺ = 632)

compound 1-57

Compound Trz25 (15 g, 41.9 mmol) and compound sub24 (8.7 g, 41.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in water (52 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of compound sub1-G-9. (Yield 61%, MS: [M+H] ⁺ = 484)

Compound sub1-G-9 (15 g, 31 mmol) and compound 1-F (7.6 g, 31 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in water (39 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of compound sub1-F-3. (Yield 62%, MS: [M+H] ⁺ = 650)

Compound sub1-F-3 (15 g, 23.1 mmol) and compound sub5 (2.8 g, 23.1 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (9.6 g, 69.2 mmol) was dissolved in water (29 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 1-57. (yield 80%, MS: [M+H] ⁺ = 692)

compound 1-58

Compound Trz26 (15 g, 33.8 mmol) and compound sub26 (5.3 g, 33.8 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (14 g, 101.4 mmol) was dissolved in water (42 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5 g of compound sub1-G-10. (Yield 60%, MS: [M+H] ⁺ = 520)

In a nitrogen atmosphere, sub1-G-10 (15 g, 28.8 mmol) and compound 1-D (7.1 g, 28.8 mmol) were placed in THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (12 g, 86.5 mmol) was dissolved in water (36 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound sub1-E-7. (yield 76%, MS: [M+H] ⁺ = 686)

Compound sub1-D-7 (15 g, 21.9 mmol) and compound sub5 (2.7 g, 21.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (9.1 g, 65.6 mmol) was dissolved in water (27 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.9 g of compound 1-58. (Yield 62%, MS: [M+H] ⁺ = 728)

compound 1-59

Compound Trz15 (15 g, 41.9 mmol) and compound sub24 (8.7 g, 41.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in water (52 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of compound sub1-G-11. (Yield 61%, MS: [M+H] ⁺ = 484)

In a nitrogen atmosphere, sub1-G-11 (15 g, 28.8 mmol) and compound 1-D (7.1 g, 28.8 mmol) were placed in THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (12 g, 86.5 mmol) was dissolved in water (36 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound sub1-E-4. (yield 76%, MS: [M+H] ⁺ = 686)

Compound sub1-F-4 (15 g, 23.1 mmol) and compound sub5 (2.8 g, 23.1 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (9.6 g, 69.2 mmol) was dissolved in water (29 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1 g of compound 1-59. (yield 76%, MS: [M+H] ⁺ = 692)

compounds 1-60

Compound Trz12 (15 g, 41.9 mmol) and compound sub28 (6.6 g, 41.9 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in water (52 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1 g of compound sub1-G-12. (Yield 61%, MS: [M+H] ⁺ = 434)

Compound sub1-G-12 (15 g, 34.6 mmol) and compound 1-D (8.5 g, 34.6 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in water (43 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of compound sub1-D-8. (yield 79%, MS: [M+H] ⁺ = 500)

Compound sub1-D-8 (15 g, 25 mmol) and compound sub10 (4.3 g, 25 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (10.4 g, 75 mmol) was dissolved in water (31 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound 1-60. (Yield 77%, MS: [M+H] ⁺ = 692)

compound 1-61

Compound Trz27 (15 g, 31.9 mmol) and compound sub9 (6.8 g, 31.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (13.2 g, 95.8 mmol) was dissolved in water (40 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10 g of compound 1-61. (Yield 52%, MS: [M+H] ⁺ = 602)

compound 1-62

Compound Trz28 (15 g, 33.8 mmol) and compound sub9 (7.2 g, 33.8 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (14 g, 101.4 mmol) was dissolved in water (42 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.8 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-62. (Yield 63%, MS: [M+H] ⁺ = 576)

compound 1-63

Compound Trz29 (15 g, 31.9 mmol) and compound sub9 (6.8 g, 31.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (13.2 g, 95.8 mmol) was dissolved in water (40 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7 g of compound 1-63. (Yield 66%, MS: [M+H] ⁺ = 602)

compound 1-64

Compound Trz30 (15 g, 31.9 mmol) and compound sub9 (6.8 g, 31.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (13.2 g, 95.8 mmol) was dissolved in water (40 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of compound 1-64. (yield 69%, MS: [M+H] ⁺ = 602)

compound 1-65

Compound Trz31 (15 g, 33.8 mmol) and compound sub9 (7.2 g, 33.8 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (14 g, 101.4 mmol) was dissolved in water (42 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.4 g, 0.8 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of compound 1-65. (yield 75%, MS: [M+H] ⁺ = 576)

compound 1-66

Compound 1-B (15 g, 60.9 mmol) and compound Trz30 (28.6 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.7 g, 1.4 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.3 g of compound sub1-B-7. (Yield 50%, MS: [M+H] ⁺ = 636)

Compound sub1-B-7 (15 g, 23.6 mmol) and compound sub5 (2.9 g, 23.6 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (9.8 g, 70.7 mmol) was dissolved in water (29 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.5 g of compound 1-66. (Yield 53%, MS: [M+H] ⁺ = 678)

compound 1-67

Compound 1-C (15 g, 60.9 mmol) and compound Trz32 (25.6 g, 60.9 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.7 g, 1.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.9 g of compound sub1-C-8. (Yield 70%, MS: [M+H] ⁺ = 586)

Compound sub1-C-8 (15 g, 25.6 mmol) and compound sub5 (3.1 g, 25.6 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (10.6 g, 76.8 mmol) was dissolved in water (32 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6 g of compound 1-67. (Yield 66%, MS: [M+H] ⁺ = 628)

compound 1-68

Compound 1-D (15 g, 60.9 mmol) and compound Trz33 (27 g, 60.9 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.7 g, 1.4 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 29.7 g of compound sub1-D-7. (Yield 80%, MS: [M+H] ⁺ = 610)

Compound sub1-D-7 (15 g, 24.6 mmol) and compound sub5 (3 g, 24.6 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in water (31 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2 g of compound 1-68. (Yield 70%, MS: [M+H] ⁺ = 652)

compound 1-69

Compound 1-E (15 g, 60.9 mmol) and compound Trz34 (24 g, 60.9 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in water (76 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.7 g, 1.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.8 g of compound sub1-E-9. (Yield 64%, MS: [M+H] ⁺ = 560)

Compound sub1-E-9 (15 g, 26.8 mmol) and compound sub5 (3.3 g, 26.8 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in water (33 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10 g of compound 1-69. (Yield 62%, MS: [M+H] ⁺ = 602)

compound 2-1

In a nitrogen atmosphere, compound 2-AA (10 g, 33.8 mmol), compound amine1 (15.1 g, 33.8 mmol), sodium tert-butoxide (10.8 g, 50.7 mmol) was added to xylene (200 ml) and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.2 g of Compound 2-1. (Yield 51%, MS: [M+H] ⁺ = 707)

compound 2-2

Compound 2-AB (10 g, 33.8 mmol), compound amine2 (12.2 g, 33.8 mmol), sodium tert-butoxide (10.8 g, 50.7 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 3 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.5 g of Compound 2-2. (Yield 50%, MS: [M+H] ⁺ = 621)

compound 2-3

Compound 2-AC (10 g, 33.8 mmol), compound amine3 (15.1 g, 33.8 mmol), sodium tert-butoxide (10.8 g, 50.7 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 3 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.1 g of compound 2-3. (Yield 55%, MS: [M+H] ⁺ = 707)

compound 2-4

Compound 2-AF (10 g, 33.8 mmol), compound amine4 (11.7 g, 33.8 mmol), sodium tert-butoxide (10.8 g, 50.7 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2 g of Compound 2-4. (Yield 55%, MS: [M+H] ⁺ = 605)

compound 2-5

Compound 2-AE (10 g, 33.8 mmol), compound amine5 (11.3 g, 33.8 mmol), sodium tert-butoxide (10.8 g, 50.7 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 3 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.4 g of Compound 2-5. (Yield 52%, MS: [M+H] ⁺ = 595)

compound 2-6

Compound 2-AE (10 g, 33.8 mmol), compound amine6 (12.6 g, 33.8 mmol), sodium tert-butoxide (10.8 g, 50.7 mmol) in xylene (200 ml) in a nitrogen atmosphere was stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 3 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.7 g of Compound 2-6. (Yield 50%, MS: [M+H] ⁺ = 631)

compound 2-7

Compound 2-AD (10 g, 33.8 mmol), compound amine7 (10 g, 33.8 mmol), sodium tert-butoxide (10.8 g, 50.7 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 3 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.9 g of Compound 2-7. (Yield 53%, MS: [M+H] ⁺ = 555)

compound 2-8

In a nitrogen atmosphere, compound 2-AA (15 g, 50.7 mmol) and compound amine8 (24.2 g, 53.2 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (21 g, 152.1 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.4 g of compound 2-8. (Yield 54%, MS: [M+H] ⁺ = 671)

compound 2-9

Compound 2-AC (15 g, 50.7 mmol) and compound amine9 (28.2 g, 53.2 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21 g, 152.1 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of compound 2-9. (Yield 55%, MS: [M+H] ⁺ = 746)

compound 2-10

Compound 2-AB (15 g, 50.7 mmol) and compound amine10 (28.2 g, 53.2 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21 g, 152.1 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.9 g of compound 2-10. (Yield 50%, MS: [M+H] ⁺ = 746)

compound 2-11

In a nitrogen atmosphere, compound 2-AD (15 g, 50.7 mmol) and compound amine 11 (23.5 g, 53.2 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (21 g, 152.1 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.3 g of compound 2-11. (Yield 55%, MS: [M+H] ⁺ = 657)

compound 2-12

Compound 2-AD (15 g, 50.7 mmol) and compound amine12 (28.8 g, 53.2 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21 g, 152.1 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.9 g of compound 2-12. (Yield 52%, MS: [M+H] ⁺ = 757)

compound 2-13

Compound 2-AE (15 g, 50.7 mmol) and compound amine13 (22.1 g, 53.2 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21 g, 152.1 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.6 g of compound 2-13. (Yield 55%, MS: [M+H] ⁺ = 632)

compound 2-14

Compound 2-AE (15 g, 50.7 mmol) and compound amine 14 (20.2 g, 53.2 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21 g, 152.1 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.6 g of compound 2-14. (Yield 55%, MS: [M+H] ⁺ = 595)

compound 2-15

Compound 2-AE (15 g, 50.7 mmol) and compound amine 11 (23.5 g, 53.2 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21 g, 152.1 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.6 g of compound 2-15. (Yield 50%, MS: [M+H] ⁺ = 657)

compound 2-16

In a nitrogen atmosphere, compound 2-AE (15 g, 50.7 mmol) and compound amine15 (28.2 g, 53.2 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (21 g, 152.1 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of compound 2-16. (Yield 55%, MS: [M+H] ⁺ = 746)

compound 2-17

Compound 2-AF (15 g, 50.7 mmol) and compound amine 16 (26.4 g, 53.2 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, stirred and refluxed. Thereafter, potassium carbonate (21 g, 152.1 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.4 g of compound 2-17. (Yield 51%, MS: [M+H] ⁺ = 711)

compound 2-18

Compound 2-AA (15 g, 50.7 mmol) and compound amine17 (31.5 g, 53.2 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21 g, 152.1 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.5 g of compound 2-18. (Yield 55%, MS: [M+H] ⁺ = 808)

compound 2-19

Compound 2-AB (15 g, 50.7 mmol) and compound amine18 (34.3 g, 53.2 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21 g, 152.1 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.2 g of compound 2-19. (Yield 51%, MS: [M+H] ⁺ = 860)

compound 2-20

Compound 2-AD (15 g, 50.7 mmol) and compound amine19 (23.5 g, 53.2 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21 g, 152.1 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17 g of compound 2-20. (Yield 51%, MS: [M+H] ⁺ = 657)

compound 2-21

Compound 2-AD (15 g, 50.7 mmol) and compound amine 20 (28.2 g, 53.2 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21 g, 152.1 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.9 g of compound 2-21. (Yield 50%, MS: [M+H] ⁺ = 784)

compound 2-22

In a nitrogen atmosphere, compound 2-AE (15 g, 50.7 mmol) and compound amine21 (22.1 g, 53.2 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (21 g, 152.1 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.9 g of compound 2-22. (Yield 53%, MS: [M+H] ⁺ = 631)

compound 2-23

In a nitrogen atmosphere, compound 2-AE (15 g, 50.7 mmol) and compound amine21 (22.1 g, 53.2 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (21 g, 152.1 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16 g of compound 2-23. (Yield 50%, MS: [M+H] ⁺ = 631)

compound 2-24

In a nitrogen atmosphere, compound 2-AH (10 g, 26.9 mmol), compound amine23 (10.7 g, 26.9 mmol), sodium tert-butoxide (8.6 g, 40.3 mmol) were added to xylene (200 ml), and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.4 g of compound 2-24. (Yield 53%, MS: [M+H] ⁺ = 734)

compound 2-25

Compound 2-AJ (10 g, 26.9 mmol), compound amine24 (12 g, 26.9 mmol), sodium tert-butoxide (8.6 g, 40.3 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2 g of Compound 2-25. (Yield 53%, MS: [M+H] ⁺ = 784)

compound 2-26

In a nitrogen atmosphere, compound 2-AJ (10 g, 26.9 mmol), compound amine25 (10 g, 26.9 mmol), sodium tert-butoxide (8.6 g, 40.3 mmol) were added to xylene (200 ml), and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.7 g of compound 2-26. (Yield 51%, MS: [M+H] ⁺ = 708)

compound 2-27

Compound 2-AK (10 g, 26.9 mmol), compound amine26 (9.4 g, 26.9 mmol), sodium tert-butoxide (8.6 g, 40.3 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.6 g of compound 2-27. (Yield 52%, MS: [M+H] ⁺ = 685)

compound 2-28

Compound 2-AI (15 g, 40.3 mmol) and compound amine27 (18.7 g, 42.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.3 g of compound 2-28. (Yield 55%, MS: [M+H] ⁺ = 734)

compound 2-29

Compound 2-AK (15 g, 40.3 mmol) and compound amine28 (15.5 g, 42.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound 2-29. (Yield 54%, MS: [M+H] ⁺ = 657)

compound 2-30

Compound 2-AG (15 g, 40.3 mmol) and compound amine29 (24 g, 42.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.3 g of compound 2-30. (Yield 50%, MS: [M+H] ⁺ = 859)

compound 2-31

Compound 2-AI (15 g, 40.3 mmol) and compound amine30 (20.8 g, 42.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.4 g of compound 2-31. (Yield 55%, MS: [M+H] ⁺ = 783)

compound 2-32

In a nitrogen atmosphere, compound 2-AJ (15 g, 40.3 mmol) and compound amine31 (21.9 g, 42.4 mmol) were added to THF (300 ml), stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.3 g of compound 2-32. (Yield 53%, MS: [M+H] ⁺ = 809)

compound 2-33

Compound 2-AK (15 g, 40.3 mmol) and compound amine32 (24 g, 42.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.7 g of compound 2-33. (Yield 51%, MS: [M+H] ⁺ = 859)

compound 2-34

Compound 2-AL (15 g, 40.3 mmol) and compound amine33 (21.9 g, 42.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.3 g of compound 2-34. (Yield 53%, MS: [M+H] ⁺ = 809)

compound 2-35

Compound 2-AI (15 g, 40.3 mmol) and compound amine34 (21.4 g, 42.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.1 g of compound 2-35. (Yield 50%, MS: [M+H] ⁺ = 797)

compound 2-36

In a nitrogen atmosphere, compound 2-AH (15 g, 40.3 mmol) and compound amine35 (21.8 g, 42.4 mmol) were added to THF (300 ml), stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.3 g of compound 2-36. (Yield 50%, MS: [M+H] ⁺ = 807)

compound 2-37

Compound 2-AQ (10 g, 28.9 mmol), compound amine36 (10.6 g, 28.9 mmol), sodium tert-butoxide (9.2 g, 43.4 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.7 g of compound 2-37. (Yield 55%, MS: [M+H] ⁺ = 675)

compound 2-38

Compound 2-AQ (10 g, 28.9 mmol), compound amine37 (12.9 g, 28.9 mmol), sodium tert-butoxide (9.2 g, 43.4 mmol) in xylene (200 ml) in a nitrogen atmosphere was stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.6 g of compound 2-38. (Yield 53%, MS: [M+H] ⁺ = 757)

compound 2-39

Compound 2-AQ (10 g, 28.9 mmol), compound amine38 (9.7 g, 28.9 mmol), sodium tert-butoxide (9.2 g, 43.4 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.7 g of compound 2-39. (Yield 52%, MS: [M+H] ⁺ = 645)

compound 2-40

Compound 2-AN (15 g, 43.4 mmol) and compound amine39 (23.6 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.3 g of compound 2-40. (Yield 51%, MS: [M+H] ⁺ = 783)

compound 2-41

Compound 2-AQ (15 g, 43.4 mmol) and compound amine27 (16.6 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of compound 2-41. (Yield 50%, MS: [M+H] ⁺ = 631)

compound 2-42

Compound 2-AR (15 g, 43.4 mmol) and compound amine 40 (20.1 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.5 g of compound 2-42. (Yield 54%, MS: [M+H] ⁺ = 707)

compound 2-43

Compound 2-AP (15 g, 43.4 mmol) and compound amine41 (26.5 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.7 g of compound 2-43. (Yield 51%, MS: [M+H] ⁺ = 847)

compound 2-44

Compound 2-AQ (15 g, 43.4 mmol) and compound amine42 (22.4 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.7 g of compound 2-44. (Yield 54%, MS: [M+H] ⁺ = 757)

compound 2-45

Compound 2-AN (15 g, 43.4 mmol) and compound amine43 (25.8 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.4 g of compound 2-45. (Yield 51%, MS: [M+H] ⁺ = 834)

compound 2-46

Compound 2-AN (15 g, 43.4 mmol) and compound amine44 (22.4 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.7 g of compound 2-46. (Yield 51%, MS: [M+H] ⁺ = 757)

compound 2-47

Compound 2-AQ (15 g, 43.4 mmol) and compound amine45 (25.8 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.1 g of compound 2-47. (Yield 53%, MS: [M+H] ⁺ = 833)

compound 2-48

In a nitrogen atmosphere, compound 2-AO (15 g, 43.4 mmol) and compound amine46 (18.9 g, 45.5 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.6 g of compound 2-48. (Yield 53%, MS: [M+H] ⁺ = 681)

compound 2-49

Compound 2-AP (15 g, 43.4 mmol) and compound amine 47 (22.4 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.7 g of compound 2-49. (Yield 54%, MS: [M+H] ⁺ = 757)

compound 2-50

Compound 2-BA (10 g, 33.9 mmol), compound amine48 (12.6 g, 33.9 mmol), sodium tert-butoxide (10.8 g, 50.8 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.3 g of Compound 2-50. (Yield 53%, MS: [M+H] ⁺ = 631)

compound 2-51

Compound 2-BA (10 g, 33.9 mmol), compound amine49 (13.5 g, 33.9 mmol), sodium tert-butoxide (10.8 g, 50.8 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.1 g of compound 2-51. (Yield 50%, MS: [M+H] ⁺ = 657)

compound 2-52

Compound 2-BC (10 g, 33.9 mmol), compound amine50 (15.6 g, 33.9 mmol), sodium tert-butoxide (10.8 g, 50.8 mmol) in xylene (200 ml) in a nitrogen atmosphere was stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.2 g of compound 2-52. (Yield 50%, MS: [M+H] ⁺ = 720)

compound 2-53

Compound 2-BB (10 g, 33.9 mmol), compound amine51 (14.4 g, 33.9 mmol), sodium tert-butoxide (10.8 g, 50.8 mmol) were placed in xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.7 g of compound 2-53. (Yield 55%, MS: [M+H] ⁺ = 684)

compound 2-54

Compound 2-BD (10 g, 33.9 mmol), compound amine52 (15.2 g, 33.9 mmol), sodium tert-butoxide (10.8 g, 50.8 mmol) in xylene (200 ml) in a nitrogen atmosphere was stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 3 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.7 g of compound 2-54. (Yield 53%, MS: [M+H] ⁺ = 707)

compound 2-55

Compound 2-BE (10 g, 33.9 mmol), compound amine53 (13.5 g, 33.9 mmol), sodium tert-butoxide (10.8 g, 50.8 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.1 g of compound 2-55. (Yield 50%, MS: [M+H] ⁺ = 657)

compound 2-56

Compound 2-BA (15 g, 50.8 mmol) and compound amine54 (25.7 g, 53.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.4 g of compound 2-56. (Yield 52%, MS: [M+H] ⁺ = 698)

compound 2-57

Compound 2-BC (15 g, 50.8 mmol) and compound amine55 (23.6 g, 53.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18 g of compound 2-57. (Yield 54%, MS: [M+H] ⁺ = 658)

compound 2-58

Compound 2-BC (15 g, 50.8 mmol) and compound amine56 (25.2 g, 53.4 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.2 g of compound 2-58. (Yield 55%, MS: [M+H] ⁺ = 687)

compound 2-59

Compound 2-BF (15 g, 50.8 mmol) and compound amine57 (31 g, 53.4 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.8 g of compound 2-59. (Yield 54%, MS: [M+H] ⁺ = 796)

compound 2-60

Compound 2-BE (15 g, 50.8 mmol) and compound amine58 (34.3 g, 53.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.8 g of compound 2-60. (Yield 50%, MS: [M+H] ⁺ = 859)

compound 2-61

In a nitrogen atmosphere, compound 2-BE (15 g, 50.8 mmol) and compound amine59 (21.1 g, 53.4 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.1 g of compound 2-61. (Yield 55%, MS: [M+H] ⁺ = 611)

compound 2-62

Compound 2-BC (15 g, 50.8 mmol) and compound amine60 (28.3 g, 53.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.7 g of compound 2-62. (Yield 52%, MS: [M+H] ⁺ = 746)

compound 2-63

Compound 2-BE (15 g, 50.8 mmol) and compound amine61 (22.2 g, 53.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.7 g of compound 2-63. (Yield 52%, MS: [M+H] ⁺ = 631)

compound 2-64

Compound 2-BD (15 g, 50.8 mmol) and compound amine62 (26.2 g, 53.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9 g of compound 2-64. (Yield 53%, MS: [M+H] ⁺ = 407)

compound 2-65

Compound 2-BD (15 g, 50.8 mmol) and compound amine63 (21.6 g, 53.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.7 g of compound 2-65. (Yield 53%, MS: [M+H] ⁺ = 621)

compound 2-66

Compound 2-BF (15 g, 50.8 mmol) and compound amine64 (29.9 g, 53.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.7 g of compound 2-66. (Yield 50%, MS: [M+H] ⁺ = 776)

compound 2-67

Compound 2-BC (15 g, 50.8 mmol) and compound amine 65 (30.3 g, 53.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.3 g of compound 2-67. (Yield 51%, MS: [M+H] ⁺ = 783)

compound 2-68

S

Compound 2-BB (15 g, 50.8 mmol) and compound amine66 (30.3 g, 53.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.5 g of compound 2-68. (Yield 54%, MS: [M+H] ⁺ = 783)

compound 2-69

Compound 2-BB (15 g, 50.8 mmol) and compound amine67 (27.6 g, 53.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.5 g of compound 2-69. (Yield 55%, MS: [M+H] ⁺ = 733)

compound 2-70

Compound 2-BF (15 g, 50.8 mmol) and compound amine68 (28.9 g, 53.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.2 g of compound 2-70. (Yield 50%, MS: [M+H] ⁺ = 757)

compound 2-71

In a nitrogen atmosphere, compound 2-BE (15 g, 50.8 mmol) and compound amine69 (30.3 g, 53.4 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.5 g of compound 2-71. (Yield 54%, MS: [M+H] ⁺ = 783)

compound 2-72

Compound 2-BC (15 g, 50.8 mmol) and compound amine70 (24.8 g, 53.4 mmol) were placed in THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.3 g of compound 2-72. (Yield 50%, MS: [M+H] ⁺ = 681)

compound 2-73

Compound 2-BF (15 g, 50.8 mmol) and compound amine71 (22.2 g, 53.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.7 g of compound 2-73. (Yield 52%, MS: [M+H] ⁺ = 631)

compound 2-74

Compound 2-BC (15 g, 50.8 mmol) and compound amine72 (37 g, 53.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.1 g of compound 2-74. (Yield 50%, MS: [M+H] ⁺ = 910)

compound 2-75

Compound 2-BD (15 g, 50.8 mmol) and compound amine73 (34.4 g, 53.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24 g of compound 2-75. (Yield 55%, MS: [M+H] ⁺ = 860)

compound 2-76

Compound 2-BG (10 g, 26.9 mmol), compound amine74 (10 g, 26.9 mmol), and sodium tert-butoxide (8.6 g, 40.3 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.4 g of compound 2-76. (Yield 55%, MS: [M+H] ⁺ = 707)

compound 2-77

Compound 2-BI (10 g, 26.9 mmol), compound amine75 (9 g, 26.9 mmol), sodium tert-butoxide (8.6 g, 40.3 mmol) in xylene (200 ml) under a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.9 g of compound 2-77. (Yield 55%, MS: [M+H] ⁺ = 671)

compound 2-78

Compound 2-BK (10 g, 26.9 mmol), compound amine76 (11.3 g, 26.9 mmol), sodium tert-butoxide (8.6 g, 40.3 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.8 g of compound 2-78. (Yield 53%, MS: [M+H] ⁺ = 757)

compound 2-79

Compound 2-BJ (10 g, 26.9 mmol), compound amine77 (10 g, 26.9 mmol), sodium tert-butoxide (8.6 g, 40.3 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.3 g of compound 2-79. (Yield 54%, MS: [M+H] ⁺ = 708)

compound 2-80

In a nitrogen atmosphere, compound 2-BJ (15 g, 40.3 mmol) and compound amine78 (15.5 g, 42.4 mmol) were added to THF (300 ml), stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound 2-80. (Yield 52%, MS: [M+H] ⁺ = 657)

compound 2-81

Compound 2-BG (15 g, 40.3 mmol) and compound amine79 (20.8 g, 42.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.7 g of compound 2-81. (Yield 53%, MS: [M+H] ⁺ = 783)

compound 2-82

Compound 2-BG (15 g, 40.3 mmol) and compound amine80 (20.8 g, 42.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.1 g of compound 2-82. (Yield 51%, MS: [M+H] ⁺ = 783)

compound 2-83

Compound 2-BI (15 g, 40.3 mmol) and compound amine81 (25.1 g, 42.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.7 g of compound 2-83. (Yield 55%, MS: [M+H] ⁺ = 889)

compound 2-84

S

In a nitrogen atmosphere, compound 2-BH (15 g, 40.3 mmol) and compound amine82 (19.3 g, 42.4 mmol) were added to THF (300 ml), stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.7 g of compound 2-84. (Yield 52%, MS: [M+H] ⁺ = 747)

compound 2-85

Compound 2-BL (15 g, 40.3 mmol) and compound amine83 (21.9 g, 42.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.3 g of compound 2-85. (Yield 53%, MS: [M+H] ⁺ = 809)

compound 2-86

Compound 2-BI (15 g, 40.3 mmol) and compound amine84 (21.4 g, 42.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.4 g of compound 2-86. (Yield 51%, MS: [M+H] ⁺ = 797)

compound 2-87

Compound 2-BG (15 g, 40.3 mmol) and compound amine85 (22.5 g, 42.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.6 g of compound 2-87. (Yield 50%, MS: [M+H] ⁺ = 823)

compound 2-88

Compound 2-BI (15 g, 40.3 mmol) and compound amine86 (21.4 g, 42.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.4 g of compound 2-88. (Yield 51%, MS: [M+H] ⁺ = 797)

compound 2-89

Compound 2-BJ (15 g, 40.3 mmol) and compound amine87 (19.7 g, 42.4 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (16.7 g, 121 mmol) was dissolved in water (50 ml), and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 1.0 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.5 g of compound 2-89. (Yield 54%, MS: [M+H] ⁺ = 757)

compound 2-90

Compound 2-BN (10 g, 28.9 mmol), compound amine88 (10.7 g, 28.9 mmol), sodium tert-butoxide (9.2 g, 43.4 mmol) in xylene (200 ml) in a nitrogen atmosphere was stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.2 g of compound 2-90. (Yield 52%, MS: [M+H] ⁺ = 681)

compound 2-91

Compound 2-BM (10 g, 28.9 mmol), compound amine89 (12.2 g, 28.9 mmol), sodium tert-butoxide (9.2 g, 43.4 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.8 g of compound 2-91. (Yield 51%, MS: [M+H] ⁺ = 731)

compound 2-92

Compound 2-BQ (10 g, 28.9 mmol), compound amine90 (11.5 g, 28.9 mmol), sodium tert-butoxide (9.2 g, 43.4 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.4 g of compound 2-92. (Yield 51%, MS: [M+H] ⁺ = 707)

compound 2-93

Compound 2-BP (10 g, 28.9 mmol), compound amine91 (11.5 g, 28.9 mmol), sodium tert-butoxide (9.2 g, 43.4 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 3 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.6 g of compound 2-93. (Yield 52%, MS: [M+H] ⁺ = 707)

compound 2-94

Compound 2-BP (15 g, 43.4 mmol) and compound amine92 (24.4 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.4 g of compound 2-94. (Yield 53%, MS: [M+H] ⁺ = 801)

compound 2-95

Compound 2-BP (15 g, 43.4 mmol) and compound amine93 (25.8 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18 g of compound 2-95. (Yield 50%, MS: [M+H] ⁺ = 833)

compound 2-96

In a nitrogen atmosphere, compound 2-BN (15 g, 43.4 mmol) and compound amine94 (24.8 g, 45.5 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19 g of compound 2-96. (Yield 54%, MS: [M+H] ⁺ = 811)

compound 2-97

Compound 2-BN (15 g, 43.4 mmol) and compound amine95 (23 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.7 g of compound 2-97. (Yield 50%, MS: [M+H] ⁺ = 909)

compound 2-98

Compound 2-BR (15 g, 43.4 mmol) and compound amine96 (20.1 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.3 g of compound 2-98. (Yield 50%, MS: [M+H] ⁺ = 707)

compound 2-99

Compound 2-BP (15 g, 43.4 mmol) and compound amine 97 (25.8 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.5 g of compound 2-99. (Yield 54%, MS: [M+H] ⁺ = 833)

compound 2-100

In a nitrogen atmosphere, compound 2-BN (15 g, 43.4 mmol) and compound amine98 (23.6 g, 45.5 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.7 g of compound 2-100. (Yield 55%, MS: [M+H] ⁺ = 783)

compound 2-101

In a nitrogen atmosphere, compound 2-BN (15 g, 43.4 mmol) and compound amine98 (23.6 g, 45.5 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 12 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.7 g of compound 2-100. (Yield 55%, MS: [M+H] ⁺ = 783)

compound 2-102

Compound 2-BP (15 g, 43.4 mmol) and compound amine100 (25.8 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 9 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.1 g of compound 2-102. (Yield 53%, MS: [M+H] ⁺ = 833)

compound 2-103

Compound 2-BO (15 g, 43.4 mmol) and compound amine101 (23 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.4 g of compound 2-103. (Yield 55%, MS: [M+H] ⁺ = 771)

compound 2-104

Compound 2-BO (15 g, 43.4 mmol) and compound amine102 (25.8 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.9 g of compound 2-104. (Yield 55%, MS: [M+H] ⁺ = 833)

compound 2-105

In a nitrogen atmosphere, compound 2-BN (15 g, 43.4 mmol) and compound amine103 (25.8 g, 45.5 mmol) were added to THF (300 ml), stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After 10 hours of reaction, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.5 g of compound 2-105. (Yield 54%, MS: [M+H] ⁺ = 833)

compound 2-106

Compound 2-AS (10 g, 33.9 mmol), compound amine104 (12.3 g, 33.9 mmol), sodium tert-butoxide (10.8 g, 50.8 mmol) were placed in xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 2 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.4 g of compound 2-106. (Yield 54%, MS: [M+H] ⁺ = 621)

compound 2-107

Compound 2-AS (15 g, 50.7 mmol) and compound amine105 (23.5 g, 53.2 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (21 g, 152.1 mmol) was dissolved in water (63 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.6 g, 1.2 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.6 g of compound 2-107. (Yield 50%, MS: [M+H] ⁺ = 657)

compound 2-108

Compound 2-BS (10 g, 33.9 mmol), compound amine106 (15.6 g, 33.9 mmol), sodium tert-butoxide (10.8 g, 50.8 mmol) in xylene (200 ml) in a nitrogen atmosphere were stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added thereto. When the reaction was completed after 3 hours, it was cooled to room temperature and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform again, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.9 g of compound 2-108. (Yield 53%, MS: [M+H] ⁺ = 720)

compound 2-109

Compound 2-BT (15 g, 43.4 mmol) and compound amine107 (24.7 g, 45.5 mmol) were added to THF (300 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.1 mmol) was dissolved in water (54 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.5 g, 1.0 mmol) was added. After the reaction for 11 hours, it was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.2 g of compound 2-109. (Yield 55%, MS: [M+H] ⁺ = 807)

[Example]

Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the thus prepared ITO transparent electrode, the following HI-1 compound was formed to a thickness of 1150 Å, but the following A-1 compound was p-doped at a concentration of 1.5 wt% to form a hole injection layer. On the hole injection layer, the following HT-1 compound was vacuum-deposited to form a hole transport layer having a thickness of 800 Å. On the hole transport layer, the following EB-1 compound was vacuum-deposited to form an electron blocking layer having a thickness of 150 Å. On the electron blocking layer, the previously prepared compound 1-2, compound 2-1, and the following Dp-7 compound were vacuum-deposited at a weight ratio of 49:49:2 to form a red light emitting layer having a thickness of 400 Å. On the light emitting layer, the following HB-1 compound was vacuum-deposited to form a hole blocking layer having a thickness of 30 Å. On the hole blocking layer, the following ET-1 compound and the following LiQ compound were vacuum-deposited at a weight ratio of 2:1 to form an electron injection and transport layer to a thickness of 300 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

In the above process, the deposition rate of organic material was maintained at 0.4~0.7 Å/sec, the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 2x10 ^-7 To maintain ~ 5x10 ^-6 torr, an organic light emitting device was manufactured.

Examples 2 to 200

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compounds shown in Tables 1 to 8 were used instead of Compound 1-2 and Compound 2-1 in preparing the emission layer.

Comparative Examples 1 to 188

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compounds shown in Tables 9 to 17 were used instead of Compound 1-2 and Compound 2-1 in preparing the emission layer. In Tables 9 to 17, compounds B-1 to B-12 and C-1 to C-16 were as follows, respectively.

When a current was applied to the organic light emitting diodes prepared in Examples and Comparative Examples, voltage and efficiency were measured (based on 15 mA/cm ² ), and the results are shown in the table below. The lifetime T95 was measured based on 7000 nits, and T95 means the time (hr) required to decrease to 95% from the initial lifetime.

	first host	second host	Driving voltage (V)	Efficiency (cd/A)	Life T95 (hr)	luminous color
Example 1	compound 1-2	compound 2-1	3.59	21.28	267	Red
Example 2	compound 1-2	compound 2-27	3.56	21.32	272	Red
Example 3	compound 1-2	compound 2-46	3.42	22.85	297	Red
Example 4	compound 1-2	compound 2-66	3.55	20.95	264	Red
Example 5	compound 1-2	compound 2-100	3.55	20.68	271	Red
Example 6	compound 1-3	compound 2-3	3.55	21.44	274	Red
Example 7	compound 1-3	compound 2-12	3.60	20.69	265	Red
Example 8	compound 1-3	compound 2-51	3.61	20.79	276	Red
Example 9	compound 1-3	compound 2-71	3.61	20.82	272	Red
Example 10	compound 1-3	compound 2-105	3.55	20.73	267	Red
Example 11	compounds 1-8	compound 2-17	3.59	20.30	274	Red
Example 12	compounds 1-8	compound 2-36	3.72	20.13	289	Red
Example 13	compounds 1-8	compound 2-51	3.63	19.66	272	Red
Example 14	compounds 1-8	compound 2-76	3.71	19.64	282	Red
Example 15	compounds 1-8	compound 2-105	3.68	20.30	278	Red
Example 16	compounds 1-9	compound 2-7	3.72	19.66	273	Red
Example 17	compounds 1-9	compound 2-41	3.59	20.50	273	Red
Example 18	compounds 1-9	compound 2-56	3.67	20.42	275	Red
Example 19	compounds 1-9	compound 2-81	3.59	19.75	280	Red
Example 20	compounds 1-9	compound 2-96	3.72	19.85	288	Red
Example 21	compounds 1-10	compound 2-1	3.58	20.98	277	Red
Example 22	compounds 1-10	compound 2-22	3.52	21.27	267	Red
Example 23	compounds 1-10	compound 2-46	3.43	22.78	293	Red
Example 24	compounds 1-10	compound 2-86	3.54	20.67	268	Red
Example 25	compounds 1-10	compound 2-96	3.51	21.23	269	Red

	first host	second host	Driving voltage (V)	Efficiency (cd/A)	Life T95 (hr)	luminous color
Example 26	compound 1-12	compound 2-3	3.51	21.43	274	Red
Example 27	compound 1-12	compound 2-27	3.43	22.89	308	Red
Example 28	compound 1-12	compound 2-51	3.50	21.49	271	Red
Example 29	compound 1-12	compound 2-91	3.53	20.77	275	Red
Example 30	compound 1-12	compound 2-105	3.61	21.09	276	Red
Example 31	compound 1-15	compound 2-1	3.85	21.29	222	Red
Example 32	compound 1-15	compound 2-27	3.44	22.50	303	Red
Example 33	compound 1-15	compound 2-56	3.92	21.63	231	Red
Example 34	compound 1-15	compound 2-96	3.89	21.14	238	Red
Example 35	compound 1-15	compound 2-105	3.90	21.53	233	Red
Example 36	compound 1-16	compound 2-12	3.91	21.28	236	Red
Example 37	compound 1-16	compound 2-36	3.86	22.02	234	Red
Example 38	compound 1-16	compound 2-61	3.85	22.09	232	Red
Example 39	compound 1-16	compound 2-91	3.85	21.92	237	Red
Example 40	compound 1-16	compound 2-105	3.92	21.24	231	Red
Example 41	compound 1-17	compound 2-2	3.71	20.66	269	Red
Example 42	compound 1-17	compound 2-28	3.73	20.74	252	Red
Example 43	compound 1-17	compound 2-47	3.82	20.64	267	Red
Example 44	compound 1-17	compound 2-67	3.74	20.73	261	Red
Example 45	compound 1-17	compound 2-101	3.70	20.52	266	Red
Example 46	compound 1-20	compound 2-13	3.82	20.71	256	Red
Example 47	compound 1-20	compound 2-32	3.76	20.52	266	Red
Example 48	compound 1-20	compound 2-52	3.72	20.65	261	Red
Example 49	compound 1-20	compound 2-72	3.76	20.69	269	Red
Example 50	compound 1-20	compound 2-106	3.80	20.51	264	Red

	first host	second host	Driving voltage (V)	Efficiency (cd/A)	Life T95 (hr)	luminous color
Example 51	compound 1-21	compound 2-18	3.60	20.89	262	Red
Example 52	compound 1-21	compound 2-37	3.46	22.23	303	Red
Example 53	compound 1-21	compound 2-52	3.60	21.19	278	Red
Example 54	compound 1-21	compound 2-77	3.57	20.99	266	Red
Example 55	compound 1-21	compound 2-106	3.52	20.96	271	Red
Example 56	compound 1-24	compound 2-8	3.59	21.47	273	Red
Example 57	compound 1-24	compound 2-42	3.59	21.29	278	Red
Example 58	compound 1-24	compound 2-57	3.61	21.24	277	Red
Example 59	compound 1-24	compound 2-82	3.54	20.72	276	Red
Example 60	compound 1-24	compound 2-97	3.60	21.38	262	Red
Example 61	compound 1-27	compound 2-2	3.66	19.81	290	Red
Example 62	compound 1-27	compound 2-23	3.71	19.98	279	Red
Example 63	compound 1-27	compound 2-47	3.69	19.65	281	Red
Example 64	compound 1-27	compound 2-87	3.71	20.11	284	Red
Example 65	compound 1-27	compound 2-97	3.68	20.56	274	Red
Example 66	compound 1-28	compound 2-13	3.41	22.57	302	Red
Example 67	compound 1-28	compound 2-28	3.45	22.50	301	Red
Example 68	compound 1-28	compound 2-52	3.91	21.54	224	Red
Example 69	compound 1-28	compound 2-92	3.88	21.91	228	Red
Example 70	compound 1-28	compound 2-106	3.80	21.78	226	Red
Example 71	compound 1-31	compound 2-2	3.80	21.63	228	Red
Example 72	compound 1-31	compound 2-28	3.90	21.71	233	Red
Example 73	compound 1-31	compound 2-57	3.92	21.42	238	Red
Example 74	compound 1-31	compound 2-97	3.93	21.25	222	Red
Example 75	compound 1-31	compound 2-106	3.81	21.39	236	Red

	first host	second host	Driving voltage (V)	Efficiency (cd/A)	Life T95 (hr)	luminous color
Example 76	compound 1-33	compound 2-13	3.41	22.61	291	Red
Example 77	compound 1-33	compound 2-37	3.48	23.40	310	Red
Example 78	compound 1-33	compound 2-62	3.86	22.07	236	Red
Example 79	compound 1-33	compound 2-92	3.88	22.18	232	Red
Example 80	compound 1-33	compound 2-106	3.86	22.20	226	Red
Example 81	compound 1-37	compound 2-4	3.40	23.29	308	Red
Example 82	compound 1-37	compound 2-29	3.82	21.75	235	Red
Example 83	compound 1-37	compound 2-48	3.93	21.85	237	Red
Example 84	compound 1-37	compound 2-68	3.85	21.90	221	Red
Example 85	compound 1-37	compound 2-102	3.81	21.56	221	Red
Example 86	compound 1-39	compound 2-14	3.42	23.04	309	Red
Example 87	compound 1-39	compound 2-33	3.86	22.10	221	Red
Example 88	compound 1-39	compound 2-53	3.85	21.97	230	Red
Example 89	compound 1-39	compound 2-73	3.89	21.91	237	Red
Example 90	compound 1-39	compound 2-107	3.80	21.97	225	Red
Example 91	compound 1-40	compound 2-19	3.90	21.97	234	Red
Example 92	compound 1-40	compound 2-38	3.82	21.59	228	Red
Example 93	compound 1-40	compound 2-53	3.87	21.33	227	Red
Example 94	compound 1-40	compound 2-78	3.91	21.80	222	Red
Example 95	compound 1-40	compound 2-107	3.85	21.60	222	Red
Example 96	compound 1-41	compound 2-9	3.74	20.89	268	Red
Example 97	compound 1-41	compound 2-43	3.82	20.60	268	Red
Example 98	compound 1-41	compound 2-58	3.76	20.68	265	Red
Example 99	compound 1-41	compound 2-83	3.82	20.71	265	Red
Example 100	compound 1-41	compound 2-98	3.82	20.66	251	Red

	first host	second host	Driving voltage (V)	Efficiency (cd/A)	Life T95 (hr)	luminous color
Example 101	compound 1-42	compound 2-4	3.47	23.36	295	Red
Example 102	compound 1-42	compound 2-24	3.82	20.52	270	Red
Example 103	compound 1-42	compound 2-48	3.72	20.45	265	Red
Example 104	compound 1-42	compound 2-88	3.81	20.82	260	Red
Example 105	compound 1-42	compound 2-98	3.79	20.64	269	Red
Example 106	compound 1-43	compound 2-14	3.44	23.36	309	Red
Example 107	compound 1-43	compound 2-29	3.54	21.34	274	Red
Example 108	compound 1-43	compound 2-53	3.53	21.42	278	Red
Example 109	compound 1-43	compound 2-93	3.54	21.22	279	Red
Example 110	compound 1-43	compound 2-107	3.55	21.40	262	Red
Example 111	compound 1-44	compound 2-4	3.42	22.62	302	Red
Example 112	compound 1-44	compound 2-29	3.49	21.12	277	Red
Example 113	compound 1-44	compound 2-58	3.52	21.01	261	Red
Example 114	compound 1-44	compound 2-98	3.52	21.10	277	Red
Example 115	compound 1-44	compound 2-107	3.49	21.58	266	Red
Example 116	compound 1-48	compound 2-14	3.46	22.91	293	Red
Example 117	compound 1-48	compound 2-38	3.87	21.63	227	Red
Example 118	compound 1-48	compound 2-63	3.92	21.63	235	Red
Example 119	compound 1-48	compound 2-93	3.48	23.30	297	Red
Example 120	compound 1-48	compound 2-107	3.82	21.22	226	Red
Example 121	compound 1-52	compound 2-5	3.80	22.04	221	Red
Example 122	compound 1-52	compound 2-30	3.88	21.20	229	Red
Example 123	compound 1-52	compound 2-49	3.79	21.29	237	Red
Example 124	compound 1-52	compound 2-69	3.88	21.40	233	Red
Example 125	compound 1-52	compound 2-103	3.89	21.96	235	Red

	first host	second host	Driving voltage (V)	Efficiency (cd/A)	Life T95 (hr)	luminous color
Example 126	compound 1-53	compound 2-15	3.45	22.62	295	Red
Example 127	compound 1-53	compound 2-34	3.46	23.27	305	Red
Example 128	compound 1-53	compound 2-54	3.61	21.35	279	Red
Example 129	compound 1-53	compound 2-74	3.55	21.55	264	Red
Example 130	compound 1-53	compound 2-108	3.60	20.72	274	Red
Example 131	compound 1-55	compound 2-20	3.56	21.02	279	Red
Example 132	compound 1-55	compound 2-39	3.41	22.71	298	Red
Example 133	compound 1-55	compound 2-54	3.49	21.02	278	Red
Example 134	compound 1-55	compound 2-79	3.50	20.71	274	Red
Example 135	compound 1-55	compound 2-108	3.61	21.35	271	Red
Example 136	compound 1-56	compound 2-10	3.80	20.77	267	Red
Example 137	compound 1-56	compound 2-44	3.71	20.58	258	Red
Example 138	compound 1-56	compound 2-59	3.75	20.52	253	Red
Example 139	compound 1-56	compound 2-84	3.74	20.82	253	Red
Example 140	compound 1-56	compound 2-99	3.79	20.74	252	Red
Example 141	compound 1-57	compound 2-5	3.70	20.50	252	Red
Example 142	compound 1-57	compound 2-25	3.79	20.54	263	Red
Example 143	compound 1-57	compound 2-49	3.77	20.42	267	Red
Example 144	compound 1-57	compound 2-89	3.76	20.51	267	Red
Example 145	compound 1-57	compound 2-99	3.75	20.57	263	Red
Example 146	compound 1-58	compound 2-15	3.59	19.85	284	Red
Example 147	compound 1-58	compound 2-30	3.65	20.43	274	Red
Example 148	compound 1-58	compound 2-54	3.70	19.88	273	Red
Example 149	compound 1-58	compound 2-94	3.60	20.10	280	Red
Example 150	compound 1-58	compound 2-108	3.67	20.09	285	Red

	first host	second host	Driving voltage (V)	Efficiency (cd/A)	Life T95 (hr)	luminous color
Example 151	compounds 1-60	compound 2-3	3.61	20.49	288	Red
Example 152	compounds 1-60	compound 2-30	3.62	20.51	284	Red
Example 153	compounds 1-60	compound 2-59	3.63	20.09	272	Red
Example 154	compounds 1-60	compound 2-99	3.65	19.66	271	Red
Example 155	compounds 1-60	compound 2-108	3.59	20.40	281	Red
Example 156	compound 1-61	compound 2-15	3.44	22.74	296	Red
Example 157	compound 1-61	compound 2-39	3.46	22.71	300	Red
Example 158	compound 1-61	compound 2-64	3.70	20.84	263	Red
Example 159	compound 1-61	compound 2-94	3.77	20.55	251	Red
Example 160	compound 1-61	compound 2-108	3.71	20.80	260	Red
Example 161	compound 1-62	compound 2-6	3.79	20.46	251	Red
Example 162	compound 1-62	compound 2-31	3.72	20.41	251	Red
Example 163	compound 1-62	compound 2-50	3.70	20.73	268	Red
Example 164	compound 1-62	compound 2-70	3.79	20.74	256	Red
Example 165	compound 1-62	compound 2-104	3.77	20.82	259	Red
Example 166	compound 1-63	compound 2-16	3.40	23.00	304	Red
Example 167	compound 1-63	compound 2-35	3.56	20.99	261	Red
Example 168	compound 1-63	compound 2-55	3.47	22.88	303	Red
Example 169	compound 1-63	compound 2-75	3.50	20.65	262	Red
Example 170	compound 1-63	compound 2-109	3.54	21.48	261	Red
Example 171	compound 1-64	compound 2-21	3.60	20.68	266	Red
Example 172	compound 1-64	compound 2-40	3.44	22.64	301	Red
Example 173	compound 1-64	compound 2-55	3.45	22.22	308	Red
Example 174	compound 1-64	compound 2-80	3.59	20.98	270	Red
Example 175	compound 1-64	compound 2-109	3.56	20.84	264	Red

	first host	second host	Driving voltage (V)	Efficiency (cd/A)	Life T95 (hr)	luminous color
Example 176	compound 1-65	compound 2-11	3.83	21.60	238	Red
Example 177	compound 1-65	compound 2-45	3.80	21.60	231	Red
Example 178	compound 1-65	compound 2-60	3.86	22.16	236	Red
Example 179	compound 1-65	compound 2-85	3.84	21.19	233	Red
Example 180	compound 1-65	compound 2-100	3.83	21.11	223	Red
Example 181	compound 1-66	compound 2-6	3.42	22.85	299	Red
Example 182	compound 1-66	compound 2-26	3.90	21.28	230	Red
Example 183	compound 1-66	compound 2-50	3.82	21.28	236	Red
Example 184	compound 1-66	compound 2-90	3.85	21.76	235	Red
Example 185	compound 1-66	compound 2-100	3.81	21.58	231	Red
Example 186	compound 1-67	compound 2-16	3.48	22.73	302	Red
Example 187	compound 1-67	compound 2-31	3.53	21.33	268	Red
Example 188	compound 1-67	compound 2-55	3.46	22.71	299	Red
Example 189	compound 1-67	compound 2-95	3.56	20.71	271	Red
Example 190	compound 1-67	compound 2-109	3.49	21.21	279	Red
Example 191	compound 1-68	compound 2-5	3.41	22.75	292	Red
Example 192	compound 1-68	compound 2-31	3.67	20.02	274	Red
Example 193	compound 1-68	compound 2-60	3.61	20.41	286	Red
Example 194	compound 1-68	compound 2-100	3.69	20.09	271	Red
Example 195	compound 1-68	compound 2-109	3.61	20.18	280	Red
Example 196	compound 1-69	compound 2-16	3.44	22.54	306	Red
Example 197	compound 1-69	compound 2-40	3.48	23.21	299	Red
Example 198	compound 1-69	compound 2-65	3.71	19.61	285	Red
Example 199	compound 1-69	compound 2-95	3.64	20.34	280	Red
Example 200	compound 1-69	compound 2-109	3.62	20.44	274	Red

	first host	second host	Driving voltage (V)	Efficiency (cd/A)	Life T95 (hr)	luminous color
Comparative Example 1	compound B-1	compound 2-1	4.09	17.95	173	Red
Comparative Example 2	compound B-1	compound 2-7	4.18	18.76	184	Red
Comparative Example 3	compound B-1	compound 2-15	4.11	18.65	186	Red
Comparative Example 4	compound B-1	compound 2-25	4.16	17.99	189	Red
Comparative Example 5	compound B-1	compound 2-32	4.17	18.62	176	Red
Comparative Example 6	compound B-2	compound 2-2	4.09	18.07	177	Red
Comparative Example 7	compound B-2	compound 2-8	4.15	18.52	185	Red
Comparative Example 8	compound B-2	compound 2-16	4.15	18.70	175	Red
Comparative Example 9	compound B-2	compound 2-26	4.18	18.14	189	Red
Comparative Example 10	compound B-2	compound 2-41	4.19	18.57	187	Red
Comparative Example 11	compound B-3	compound 2-3	4.19	18.58	185	Red
Comparative Example 12	compound B-3	compound 2-9	4.15	18.60	185	Red
Comparative Example 13	compound B-3	compound 2-17	4.15	17.91	172	Red
Comparative Example 14	compound B-3	compound 2-27	4.15	18.28	176	Red
Comparative Example 15	compound B-3	compound 2-34	4.17	18.05	185	Red
Comparative Example 16	compound B-4	compound 2-4	4.34	16.58	137	Red
Comparative Example 17	compound B-4	compound 2-10	4.32	13.96	138	Red
Comparative Example 18	compound B-4	compound 2-18	4.38	13.27	133	Red
Comparative Example 19	compound B-4	compound 2-28	4.36	14.11	134	Red
Comparative Example 20	compound B-4	compound 2-43	4.39	13.78	127	Red
Comparative Example 21	compound B-5	compound 2-5	4.29	17.67	153	Red
Comparative Example 22	compound B-5	compound 2-11	4.15	17.81	142	Red
Comparative Example 23	compound B-5	compound 2-19	4.18	18.07	168	Red
Comparative Example 24	compound B-5	compound 2-29	4.11	17.98	170	Red
Comparative Example 25	compound B-5	compound 2-36	4.11	17.84	141	Red

	first host	second host	Driving voltage (V)	Efficiency (cd/A)	Life T95 (hr)	luminous color
Comparative Example 26	compound B-6	compound 2-6	4.34	13.52	93	Red
Comparative Example 27	compound B-6	compound 2-12	4.32	13.96	102	Red
Comparative Example 28	compound B-6	compound 2-20	4.38	13.27	83	Red
Comparative Example 29	compound B-6	compound 2-30	4.36	14.11	84	Red
Comparative Example 30	compound B-6	compound 2-45	4.39	13.78	87	Red
Comparative Example 31	compound B-7	compound 2-1	4.14	17.96	169	Red
Comparative Example 32	compound B-7	compound 2-7	4.15	17.82	186	Red
Comparative Example 33	compound B-7	compound 2-15	4.20	18.69	177	Red
Comparative Example 34	compound B-7	compound 2-25	4.15	18.33	189	Red
Comparative Example 35	compound B-7	compound 2-32	4.14	18.53	180	Red
Comparative Example 36	compound B-8	compound 2-2	4.29	13.40	103	Red
Comparative Example 37	compound B-8	compound 2-8	4.29	14.35	95	Red
Comparative Example 38	compound B-8	compound 2-16	4.41	14.45	86	Red
Comparative Example 39	compound B-8	compound 2-26	4.39	14.46	87	Red
Comparative Example 40	compound B-8	compound 2-41	4.36	14.21	94	Red
Comparative Example 41	compound B-9	compound 2-3	4.10	18.60	187	Red
Comparative Example 42	compound B-9	compound 2-9	4.18	18.09	188	Red
Comparative Example 43	compound B-9	compound 2-17	4.15	18.64	169	Red
Comparative Example 44	compound B-9	compound 2-27	4.20	18.35	190	Red
Comparative Example 45	compound B-9	compound 2-34	4.16	17.83	181	Red
Comparative Example 46	compound B-10	compound 2-4	4.42	17.48	139	Red
Comparative Example 47	compound B-10	compound 2-10	4.39	14.28	140	Red
Comparative Example 48	compound B-10	compound 2-18	4.30	14.40	131	Red
Comparative Example 49	compound B-10	compound 2-28	4.39	13.98	127	Red
Comparative Example 50	compound B-10	compound 2-43	4.32	14.24	129	Red

	first host	second host	Driving voltage (V)	Efficiency (cd/A)	Life T95 (hr)	luminous color
Comparative Example 51	compound B-11	compound 2-5	4.22	17.24	167	Red
Comparative Example 52	compound B-11	compound 2-11	4.14	17.67	167	Red
Comparative Example 53	compound B-11	compound 2-19	4.13	18.06	167	Red
Comparative Example 54	compound B-11	compound 2-29	4.21	17.20	162	Red
Comparative Example 55	compound B-11	compound 2-36	4.19	18.03	144	Red
Comparative Example 56	compound B-12	compound 2-6	4.11	18.09	151	Red
Comparative Example 57	compound B-12	compound 2-12	4.18	17.44	145	Red
Comparative Example 58	compound B-12	compound 2-20	4.15	18.08	137	Red
Comparative Example 59	compound B-12	compound 2-30	4.09	18.03	144	Red
Comparative Example 60	compound B-12	compound 2-45	4.36	14.10	103	Red

	first host	second host	Driving voltage (V)	Efficiency (cd/A)	Life T95 (hr)	luminous color
Comparative Example 61	compound 2-1	compound C-1	4.41	14.17	96	Red
Comparative Example 62	compound 2-27	compound C-1	4.30	13.47	101	Red
Comparative Example 63	compound 2-46	compound C-1	4.35	13.93	103	Red
Comparative Example 64	compound 2-66	compound C-1	4.39	13.85	97	Red
Comparative Example 65	compound 2-3	compound C-1	4.41	13.95	95	Red
Comparative Example 66	compound 2-12	compound C-1	4.31	13.82	95	Red
Comparative Example 67	compound 2-51	compound C-1	4.30	14.18	85	Red
Comparative Example 68	compound 2-71	compound C-1	4.30	14.22	102	Red
Comparative Example 69	compound 2-17	compound C-2	4.40	13.83	102	Red
Comparative Example 70	compound 2-36	compound C-2	4.34	13.49	94	Red
Comparative Example 71	compound 2-51	compound C-2	4.30	13.94	102	Red
Comparative Example 72	compound 2-76	compound C-2	4.31	13.71	84	Red
Comparative Example 73	compound 2-105	compound C-2	4.41	13.34	96	Red
Comparative Example 74	compound 2-7	compound C-2	4.30	14.03	85	Red
Comparative Example 75	compound 2-41	compound C-2	4.30	13.25	82	Red
Comparative Example 76	compound 2-56	compound C-2	4.33	13.41	104	Red
Comparative Example 77	compound 2-1	compound C-3	4.41	13.57	95	Red
Comparative Example 78	compound 2-22	compound C-3	4.38	14.26	94	Red
Comparative Example 79	compound 2-46	compound C-3	4.35	13.44	88	Red
Comparative Example 80	compound 2-86	compound C-3	4.40	13.28	100	Red
Comparative Example 81	compound 2-96	compound C-3	4.35	13.88	92	Red
Comparative Example 82	compound 2-5	compound C-3	4.41	13.63	103	Red
Comparative Example 83	compound 2-25	compound C-3	4.31	14.42	85	Red
Comparative Example 84	compound 2-49	compound C-3	4.42	13.24	93	Red

	first host	second host	Driving voltage (V)	Efficiency (cd/A)	Life T95 (hr)	luminous color
Comparative Example 85	compound 2-4	compound C-4	4.41	17.28	136	Red
Comparative Example 86	compound 2-24	compound C-4	4.38	14.26	130	Red
Comparative Example 87	compound 2-48	compound C-4	4.35	13.44	130	Red
Comparative Example 88	compound 2-88	compound C-4	4.40	13.28	131	Red
Comparative Example 89	compound 2-98	compound C-4	4.35	13.88	139	Red
Comparative Example 90	compound 2-14	compound C-4	4.41	13.63	140	Red
Comparative Example 91	compound 2-29	compound C-4	4.31	14.42	128	Red
Comparative Example 92	compound 2-53	compound C-4	4.42	13.24	131	Red
Comparative Example 93	compound 2-1	compound C-5	4.34	16.56	129	Red
Comparative Example 94	compound 2-27	compound C-5	4.30	14.33	127	Red
Comparative Example 95	compound 2-46	compound C-5	4.41	13.77	127	Red
Comparative Example 96	compound 2-66	compound C-5	4.40	13.94	129	Red
Comparative Example 97	compound 2-3	compound C-5	4.37	14.42	137	Red
Comparative Example 98	compound 2-12	compound C-5	4.33	13.62	140	Red
Comparative Example 99	compound 2-51	compound C-5	4.34	14.10	129	Red
Comparative Example 100	compound 2-71	compound C-5	4.41	14.08	136	Red
Comparative Example 101	compound 2-17	compound C-6	4.40	16.50	135	Red
Comparative Example 102	compound 2-36	compound C-6	4.32	13.20	139	Red
Comparative Example 103	compound 2-51	compound C-6	4.40	14.04	138	Red
Comparative Example 104	compound 2-76	compound C-6	4.29	14.15	136	Red
Comparative Example 105	compound 2-105	compound C-6	4.33	14.31	136	Red
Comparative Example 106	compound 2-7	compound C-6	4.37	14.14	138	Red
Comparative Example 107	compound 2-41	compound C-6	4.36	13.70	127	Red
Comparative Example 108	compound 2-56	compound C-6	4.36	13.54	132	Red

	first host	second host	Driving voltage (V)	Efficiency (cd/A)	Life T95 (hr)	luminous color
Comparative Example 109	compound 2-1	compound C-7	4.11	18.54	177	Red
Comparative Example 110	compound 2-22	compound C-7	4.12	18.37	176	Red
Comparative Example 111	compound 2-46	compound C-7	4.13	18.79	182	Red
Comparative Example 112	compound 2-86	compound C-7	4.12	18.26	175	Red
Comparative Example 113	compound 2-96	compound C-7	4.13	18.23	168	Red
Comparative Example 114	compound 2-5	compound C-7	4.14	18.84	168	Red
Comparative Example 115	compound 2-25	compound C-7	4.21	18.36	174	Red
Comparative Example 116	compound 2-49	compound C-7	4.17	18.80	187	Red
Comparative Example 117	compound 2-4	compound C-8	4.10	18.52	184	Red
Comparative Example 118	compound 2-24	compound C-8	4.12	18.53	169	Red
Comparative Example 119	compound 2-48	compound C-8	4.11	18.77	178	Red
Comparative Example 120	compound 2-88	compound C-8	4.19	18.48	186	Red
Comparative Example 121	compound 2-98	compound C-8	4.17	18.56	172	Red
Comparative Example 122	compound 2-14	compound C-8	4.19	18.82	170	Red
Comparative Example 123	compound 2-29	compound C-8	4.21	18.74	181	Red
Comparative Example 124	compound 2-53	compound C-8	4.11	18.35	181	Red
Comparative Example 125	compound 2-1	compound C-9	4.30	18.09	162	Red
Comparative Example 126	compound 2-27	compound C-9	4.15	17.47	159	Red
Comparative Example 127	compound 2-46	compound C-9	4.21	17.71	156	Red
Comparative Example 128	compound 2-66	compound C-9	4.16	17.59	137	Red
Comparative Example 129	compound 2-3	compound C-9	4.21	17.80	159	Red
Comparative Example 130	compound 2-12	compound C-9	4.15	17.36	139	Red
Comparative Example 131	compound 2-51	compound C-9	4.18	18.03	170	Red
Comparative Example 132	compound 2-71	compound C-9	4.10	17.38	143	Red

	first host	second host	Driving voltage (V)	Efficiency (cd/A)	Life T95 (hr)	luminous color
Comparative Example 133	compound 2-17	compound C-10	4.10	17.81	189	Red
Comparative Example 134	compound 2-36	compound C-10	4.20	17.85	181	Red
Comparative Example 135	compound 2-51	compound C-10	4.11	17.87	171	Red
Comparative Example 136	compound 2-76	compound C-10	4.14	18.38	185	Red
Comparative Example 137	compound 2-105	compound C-10	4.12	18.28	180	Red
Comparative Example 138	compound 2-7	compound C-10	4.12	18.34	186	Red
Comparative Example 139	compound 2-41	compound C-10	4.17	18.19	173	Red
Comparative Example 140	compound 2-56	compound C-10	4.11	18.84	185	Red
Comparative Example 141	compound 2-1	compound C-11	4.35	16.30	128	Red
Comparative Example 142	compound 2-22	compound C-11	4.42	14.24	139	Red
Comparative Example 143	compound 2-46	compound C-11	4.35	13.61	140	Red
Comparative Example 144	compound 2-86	compound C-11	4.29	14.28	139	Red
Comparative Example 145	compound 2-96	compound C-11	4.32	13.74	136	Red
Comparative Example 146	compound 2-5	compound C-11	4.38	13.51	128	Red
Comparative Example 147	compound 2-25	compound C-11	4.38	13.76	140	Red
Comparative Example 148	compound 2-49	compound C-11	4.33	14.50	138	Red
Comparative Example 149	compound 2-4	compound C-12	4.22	18.02	162	Red
Comparative Example 150	compound 2-24	compound C-12	4.21	17.51	145	Red
Comparative Example 151	compound 2-48	compound C-12	4.10	17.53	164	Red
Comparative Example 152	compound 2-88	compound C-12	4.16	17.46	146	Red
Comparative Example 153	compound 2-98	compound C-12	4.15	17.79	156	Red
Comparative Example 154	compound 2-14	compound C-12	4.14	17.35	141	Red
Comparative Example 155	compound 2-29	compound C-12	4.09	17.73	136	Red
Comparative Example 156	compound 2-53	compound C-12	4.19	17.72	169	Red

	first host	second host	Driving voltage (V)	Efficiency (cd/A)	Life T95 (hr)	luminous color
Comparative Example 157	compound 2-1	compound C-13	4.40	14.12	85	Red
Comparative Example 158	compound 2-27	compound C-13	4.39	13.82	83	Red
Comparative Example 159	compound 2-46	compound C-13	4.29	13.48	88	Red
Comparative Example 160	compound 2-66	compound C-13	4.39	13.78	99	Red
Comparative Example 161	compound 2-3	compound C-13	4.33	13.58	92	Red
Comparative Example 162	compound 2-12	compound C-13	4.31	13.48	83	Red
Comparative Example 163	compound 2-51	compound C-13	4.32	13.37	101	Red
Comparative Example 164	compound 2-71	compound C-13	4.34	14.04	102	Red
Comparative Example 165	compound 2-17	compound C-14	4.37	17.40	135	Red
Comparative Example 166	compound 2-36	compound C-14	4.38	13.51	128	Red
Comparative Example 167	compound 2-51	compound C-14	4.32	14.35	135	Red
Comparative Example 168	compound 2-76	compound C-14	4.40	13.95	129	Red
Comparative Example 169	compound 2-105	compound C-14	4.33	13.50	128	Red
Comparative Example 170	compound 2-7	compound C-14	4.33	13.34	133	Red
Comparative Example 171	compound 2-41	compound C-14	4.39	13.20	129	Red
Comparative Example 172	compound 2-56	compound C-14	4.34	13.46	128	Red
Comparative Example 173	compound 2-1	compound C-15	4.13	18.40	168	Red
Comparative Example 174	compound 2-22	compound C-15	4.13	17.91	173	Red
Comparative Example 175	compound 2-46	compound C-15	4.12	18.31	186	Red
Comparative Example 176	compound 2-86	compound C-15	4.16	18.04	186	Red
Comparative Example 177	compound 2-96	compound C-15	4.11	18.51	179	Red
Comparative Example 178	compound 2-5	compound C-15	4.18	17.92	186	Red
Comparative Example 179	compound 2-25	compound C-15	4.12	18.34	172	Red
Comparative Example 180	compound 2-49	compound C-15	4.09	18.41	186	Red

	first host	second host	Driving voltage (V)	Efficiency (cd/A)	Life T95 (hr)	luminous color
Comparative Example 181	compound 2-4	compound C-16	4.09	18.70	183	Red
Comparative Example 182	compound 2-24	compound C-16	4.19	18.23	181	Red
Comparative Example 183	compound 2-48	compound C-16	4.14	18.75	172	Red
Comparative Example 184	compound 2-88	compound C-16	4.20	18.06	179	Red
Comparative Example 185	compound 2-98	compound C-16	4.15	18.41	169	Red
Comparative Example 186	compound 2-14	compound C-16	4.16	18.52	185	Red
Comparative Example 187	compound 2-29	compound C-16	4.20	18.20	180	Red
Comparative Example 188	compound 2-53	compound C-16	4.18	17.88	168	Red

When a current was applied to the organic light emitting diodes fabricated in Examples 1 to 200 and Comparative Examples 1 to 188, the results shown in the above table were obtained. The red organic light emitting device of Example 1 used a material widely used in the prior art, and has a structure using compound EB-1 as an electron blocking layer and Dp-7 as a dopant in the red light emitting layer. Comparative Example Compounds B-1 to B-12 and when used as a red light emitting layer by co-evaporation like the compound of Formula 2 of the present invention, the driving voltage generally increased and the efficiency and lifespan decreased compared to the combination of the present invention, When used as a red light emitting layer by co-deposition like the compounds of Comparative Examples C-1 to C-16 and the compound of Formula 1 of the present invention, the driving voltage increased and the efficiency and lifespan decreased.

When inferred from these results, the reason that the driving voltage is improved and the efficiency and lifespan are increased is that the combination of the compound of Formula 1 as the first host and the compound of Formula 2 as the second host of the present invention is energy as a red dopant in the red light emitting layer. It can be seen that the transfer is going well. In the end, it was confirmed that the combination of Chemical Formula 1 and Chemical Formula 2 of the present invention, rather than the combination with the Comparative Example compound, combines electrons and holes to form excitons through a more stable balance into the light emitting layer, thereby greatly increasing efficiency and lifetime. In conclusion, it can be confirmed that the driving voltage, luminous efficiency and lifespan characteristics of the organic light emitting device can be improved when the compound of Formula 1 and the compound of Formula 2 are combined and used as a host for the red light emitting layer by co-evaporation.

[Explanation of code]

1: Substrate 2: Anode

3: light emitting layer 4: cathode

5: hole injection layer 6: hole transport layer

7: light emitting layer 8: electron transport layer

Claims (11)

1. anode,

   cathode, and

   a light emitting layer between the anode and the cathode;

   The light emitting layer comprises (i) a compound represented by the following Chemical Formula 1, and (ii) a compound represented by the following Chemical Formula 2 or Chemical Formula 3,

   Organic light emitting device:

   [Formula 1]

   

   In Formula 1,

   L is a single bond; Or a substituted or unsubstituted C _6-60 arylene,

   X is N; or CH, with the proviso that at least two or more of X are N;

   R is hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising any one or more selected from the group consisting of N, O and S,

   Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _2-60 heteroaryl comprising any one or more selected from the group consisting of N, O and S,

   [Formula 2]

   

   [Formula 3]

   

   In Formulas 2 and 3,

   R' is a substituent represented by the following formula (4), or a substituted or unsubstituted C _6-60 aryl,

   When R' is a substituent represented by the following formula (4), R' ₁ to R' ₆ are each independently hydrogen or deuterium;

   When R' is not a substituent represented by the following formula (4), one of R' ₁ to R' ₆ is a substituent represented by the following formula (4), and the rest are each independently hydrogen or deuterium;

   [Formula 4]

   

   In Formula 4,

   L' is a single bond, a substituted or unsubstituted C _6-60 arylene, or a substituted or unsubstituted C _2-60 heteroarylene comprising at least one selected from the group consisting of N, O and S; ,

   L' ₁ and L' ₂ are each independently selected from the group consisting of a single bond, substituted or unsubstituted C _6-60 arylene, or substituted or unsubstituted N, O and S. is C _2-60 heteroarylene,

   Ar' ₁ and Ar' ₂ are each independently, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _2- containing at least one selected from the group consisting of N, O and S ₆₀ heteroaryl.
2. According to claim 1,

   L is a single bond; phenylene; biphenyldiyl; or naphthylene,

   organic light emitting device.
3. According to claim 1,

   X is all N;

   organic light emitting device.
4. According to claim 1,

   R is hydrogen, deuterium, phenyl, biphenylyl, terphenylyl, naphthyl, phenylnaphthyl, naphthylphenyl, phenanthrenyl, triphenylenyl, fluoranthenyl, dibenzofuranyl, benzonaphthofuranyl, di which is benzothiophenyl, or benzonaphthothiophenyl;

   organic light emitting device.
5. According to claim 1,

   Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, naphthylphenyl, phenylnaphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl;

   organic light emitting device.
6. According to claim 1,

   The compound represented by Formula 1 is any one selected from the group consisting of

   Organic light emitting device:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   
7. According to claim 1,

   R' is a substituent represented by Formula 4, or phenyl, biphenyl, or naphthyl;

   organic light emitting device.
8. According to claim 1,

   L' is a single bond, phenylene, biphenyldiyl, terphenyldiyl, naphthylene, or -(phenylene)-(naphthylene)-;

   organic light emitting device.
9. According to claim 1,

   L' ₁ and L' ₂ are each independently a single bond, phenylene, or biphenyldiyl,

   organic light emitting device.
10. According to claim 1,

    Ar' ₁ and Ar' ₂ are each independently, phenyl, biphenylyl, terphenylyl, naphthyl, naphthylphenyl, phenylnaphthyl, phenanthrenyl, dimethylfluorenyl, diphenylfluorenyl, dibenzo furanyl, dibenzothiophenyl, 9H-carbazol-9-yl, or 9-phenyl-9H-carbazole;

    organic light emitting device.
11. According to claim 1,

    The compound represented by Formula 2 or Formula 3 is any one selected from the group consisting of

    Organic light emitting device:

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

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