KR20220121218A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting element with increased driving voltage, efficiency and lifetime. The organic light emitting element includes an anode, a cathode, and a light emitting layer between the anode and the cathode. The organic light emitting element has excellent driving voltage, efficiency and lifetime.

Description

Organic light emitting device

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

[Technology behind the invention]

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.

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.

또는

는 다른 치환기에 연결되는 결합을 의미한다. 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; a 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, in which two or more substituents of the above-exemplified substituents are connected . 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.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.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 preferable. 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. 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 12.2 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. 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 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

질소 분위기에서 화합물 Trz3(15 g, 47.2 mmol)와 화합물 sub24(9.7 g, 47.2 mmol)를 THF(300 ml)에 넣고 교반 및 환류하였다. 이 후 포타슘 카보네이트(19.6 g, 141.6 mmol)를 물(59 ml)에 녹여 투입하고 충분히 교반한 후 비스(트리-터트-부틸포스핀)팔라듐(0)(0.2 g, 0.4 mmol)을 투입하였다. 11시간 반응 후 상온으로 식히고 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시 클로로포름에 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수 황산 마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제하여 화합물 sub1-G-1를 13 g 제조하였다. (수율 62%, MS: [M+H]⁺= 444)

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

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

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 0.3Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 2×10 ^-7 ~ 5×10 ^-6 torr was maintained, and 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.

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)

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.
According to claim 1,
L is a single bond; phenylene; biphenyldiyl; or naphthylene,
organic light emitting device.
According to claim 1,
X is all N;
organic light emitting device.
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.
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.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
Organic light emitting device:

According to claim 1,
R' is a substituent represented by Formula 4, or phenyl, biphenyl, or naphthyl;
organic light emitting device.
According to claim 1,
L' is a single bond, phenylene, biphenyldiyl, terphenyldiyl, naphthylene, or -(phenylene)-(naphthylene)-;
organic light emitting device.
According to claim 1,
L' ₁ and L' ₂ are each independently a single bond, phenylene, or biphenyldiyl,
organic light emitting device.
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.
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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