CN112047802B

CN112047802B - Polysubstituted ethylene compound, preparation method and application thereof

Info

Publication number: CN112047802B
Application number: CN201910485350.4A
Authority: CN
Inventors: 林国强; 唐本忠; 冯陈国; 秦安军; 李梦尧; 胡天骄; 韩鹏博
Original assignee: Shanghai Institute of Organic Chemistry of CAS
Current assignee: Shanghai Institute of Organic Chemistry of CAS
Priority date: 2019-06-05
Filing date: 2019-06-05
Publication date: 2022-07-19
Anticipated expiration: 2039-06-05
Also published as: CN112047802A

Abstract

The invention discloses a polysubstituted ethylene compound and a preparation method thereofAnd applications. The invention specifically discloses a preparation method of a polysubstituted ethylene compound shown as a formula III, which comprises the following steps: in an organic solvent, a compound shown as a formula I and a compound shown as a formula II are subjected to a reaction shown as follows in the presence of a palladium catalyst, a phosphine ligand and alkali to obtain a polysubstituted ethylene compound shown as a formula III. The preparation method can be suitable for various substrates, and the configuration of double bonds is controllable.

Description

Polysubstituted ethylene compound, preparation method and application thereof

Technical Field

The invention relates to the field of chemistry, and particularly relates to a polysubstituted ethene compound, and a preparation method and application thereof.

Background

Substituted ethenes are widely present in natural products, active pharmaceutical intermediates and luminescent materials. Among them, the polyarylate substituted ethylene skeleton has been widely studied because of having an Aggregation Induced Emission (AIE) effect. In 2001, the Tang group discovered for the first time the aggregation-induced emission properties of silole compounds. Subsequently, cyano-substituted stilbene (CN-BPE), triphenylethylene (trise), and Tetraphenylethylene (TPE) compounds have been extensively studied due to their simple and stable molecular structure, simple synthesis steps, and significant AIE effect.

In 2002, subject group of Park et al (j.am. chem.soc.,2002,124,14410.) found that 1-cyano-trans-1, 2-bis (4-methylbiphenyl) ethylene (CN-MBE) had an aggregation-induced fluorescence enhancement (AIEE) effect. Subsequently, the cyanostilbene scaffolds have very broad applications in chemical sensing (Talanta,2013,107,332.), cellular imaging (j.mater.chem.b,2016,4,2614.), and stimulation response (j.am.chem.soc, 2010,132,13675).

In 2008, the Tang group (appl. phy. lett.2007,91,011111.) obtained a tetraphenylethylene backbone by Mcmurry olefination and found it to have significant AIE properties. Subsequently, the TPE framework as a light emitting layer has very wide application in deep blue OLED materials. Zhao et al, topic group (chem.commun.,2010,46,686.) butt-jointed two TPEs, and a sky blue OLED material was constructed using a TPE-TPE structure as a light emitting layer. In 2011, the Tang group (chem.mater.2011,23,2536.) introduced triphenylamine and other groups with charge transport properties into TPE, and the compounds were used as both light-emitting layer and hole transport layer to construct deep blue light-emitting OLED material, which is better than OLED material with additional hole transport layer.

In 2009, the Chi project group (j. mater. chem.,2009,19,5541.) found that the triphenylethylene (TriPE) -based skeleton was a blue-light material with AIE effect. In 2018, the Tang project group (adv.funct.mater, 2018,28, 1705609) designed and synthesized organic field effect transistor material (OFET) substituted by poly Perylenetetracarboxylic Diimide (PDI) with triphenylethylene (TriPE) as a framework, and the molecules have high quantum efficiency and electron mobility.

For multi-substituted ethylene compounds, the cis-trans of the carbon-carbon double bond has a great influence on the luminous properties of the compounds. In 2006, the Ma topic group (j.phys.chem.b., 2006,20999) studied the effect of cis-trans luminescence properties of the double bond of 1, 2-diaryl-substituted olefin-based compounds (cis-DPDSB/trans-DPDSB).

At present, the known method for synthesizing the polysubstituted ethylene mainly comprises a Wittig reaction, a Mcmmurry olefination reaction and a coupling reaction in which a transition metal participates. For the coupling of transition metal, firstly, a metal aryl species is formed by means of oxidation addition of aryl halide, transmetalization of aryl boron reagent, aryl metal reagent and transition metal, guide group mediated C-H bond activation and the like, and then the metal aryl species and an alkyne compound carry out an alkyne insertion reaction or a Heck reaction with 1, 1-disubstituted olefin and 1, 2-disubstituted olefin, so as to obtain a polysubstituted ethylene compound, but the configuration of a double bond is not easy to control. For multi-substituted ethylene compounds, the Z/E isomers are often similar in polarity and difficult to separate.

Disclosure of Invention

The invention aims to solve the technical problem of providing a polysubstituted ethylene compound, and a preparation method and application thereof. The preparation method of the invention can be suitable for various substrates, and the configuration of double bonds is controllable.

The invention provides a preparation method of a polysubstituted ethene compound shown as a formula III, which comprises the following steps: in an organic solvent, carrying out the following reaction on a compound shown as a formula I and a compound shown as a formula II in the presence of a palladium catalyst, a phosphine ligand and alkali to obtain a polysubstituted ethylene compound shown as a formula III;

wherein ring A is C_6-16Aromatic rings (e.g. C)_6-14An aromatic ring, such as a benzene ring or a naphthalene ring) or a 5-16 membered heteroaromatic ring (e.g., a 5-10 membered heteroaromatic ring, such as a pyridine ring);

each R³Independently of one another is fluorine, chlorine, cyano, C_1-6Alkyl (e.g. methyl), C_3-6Cycloalkyl, C_1-6Alkoxy (e.g. methoxy), C_3-6Cycloalkoxy or C_1-6Haloalkyl (e.g., trifluoromethyl);

m is 0,1, 2, 3 or 4;

x is Br, I or OTf;

R¹is C_1-6Alkyl (e.g., isopropyl), cyano, and,

(e.g. in the case of

)、C_6-16Aryl (e.g. C)_6-14Aryl, e.g. phenyl or naphthyl) or 5-16 membered heteroaryl (e.g. 5-10 membered heteroaryl, e.g. thienyl), C_6-16Aryl or 5-16 membered heteroaryl optionally substituted with one or more (e.g. 1,2, 3 or 4) R^1-1Substituted, wherein each R^1-1Each independently of the others being fluorine, chlorine, cyano, C_1-6Alkyl (e.g. methyl), C_3-6Cycloalkyl, C_1-6Alkoxy (e.g. methoxy), C_3-6Cycloalkoxy or C_1-6Haloalkyl (e.g., trifluoromethyl);

R⁶is C_1-6An alkyl group;

ring B is C_6-16Aromatic rings (e.g. C)_6-14An aromatic ring, such as a benzene ring, a naphthalene ring, an anthracene ring, or a pyrene ring) or a 5-16 membered heteroaromatic ring (e.g., a 5-10 membered heteroaromatic ring, such as a furan ring, a thiophene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a benzopyridine ring, or a benzofuran ring);

each R⁵Each independently of the other is fluorine, chlorine, C_1-6Alkyl (e.g. methyl), C_3-6Cycloalkyl, C_1-6Alkoxy (e.g. methoxy), C_3-6Cycloalkoxy, cyano, nitroA group, an aldehyde group, an amino group,

(e.g. trimethylsilyl),

(e.g. in the case of

)、

(e.g. in

)、

(e.g. in

)、

(e.g. in the case of

) Or C_1-6Haloalkyl (e.g., trifluoromethyl); wherein R is^2-2、R^2-3、R^2-4、R² ^-5、R^2-6、R^2-7、R^2-8、R^2-9、R^2-10And R^2-11Each independently is C_1-6An alkyl group;

n is 0,1, 2, 3 or 4;

R⁴is composed of

(e.g. in the case of

)、

(e.g. in the case of

)、

Wherein R is⁵¹、R⁵²、R⁵³、R⁵⁴、R⁵⁵、R⁵⁶、R⁵⁷、R⁵⁸、R⁵⁹、R⁶⁰、R⁶¹And R⁶²Each independently is hydrogen or C_1-6An alkyl group;

the heteroatoms in the heteroaromatic ring or heteroaryl group are each independently nitrogen, oxygen or sulfur, and the number of heteroatoms is independently 1,2, 3 or 4.

At R³、R¹、R⁶、R⁵、R^1-1、R^2-2、R^2-3、R^2-4、R^2-5、R^2-6、R^2-7、R^2-8、R^2-9、R^2-10、R^2-11、R⁵¹、R⁵²、R⁵³、R⁵⁴、R⁵⁵、R⁵⁶、R⁵⁷、R⁵⁸、R⁵⁹、R⁶⁰、R⁶¹And R⁶²In (b), the C_1-6The alkyl groups may each independently be C_1-4An alkyl group.

At R³、R⁵And R^1-1In (b), the C_1-6The alkoxy groups may each independently be C_1-4An alkoxy group.

At R³、R⁵And R^1-1In (b), the C_1-6The haloalkyl groups may each independently be C_1-4A haloalkyl group. In some embodiments of the invention, the halogen in the haloalkyl is fluorine.

In some embodiments of the invention, X is Br.

In some aspects of the inventionIn the table, R¹Is C_1-6Alkyl, cyano, or,

Wherein each R⁶And R^1-1Each independently as defined herein, and each z is each independently 0,1, 2, 3 or 4.

In some embodiments of the invention, R¹Is any one of the following structures:

wherein each R is^1-1Each independently as defined herein.

in some embodiments of the present invention, the compound of formula I is selected from any of the following structures:

wherein each X, R¹、R³And m are each independently as defined herein.

wherein each X, R¹And R³Each independently as defined herein.

wherein each X, R¹And R³Each independently as defined herein.

in some embodiments of the present invention, the compound of formula II is selected from any of the following structures:

wherein each R is⁴、R⁵And n are each independently as defined herein.

wherein each R is⁴And R⁵Each independently as defined herein.

wherein each R is⁴Each independently of the otherAs defined in the present invention.

In some embodiments of the invention, R⁴Is composed of

In some embodiments of the invention, R⁴Is composed of

In some embodiments of the invention, R⁴Is composed of

in some embodiments of the invention, the compound of formula III is of any of the following structures:

in some embodiments of the invention, the compounds of formula I, formula II, and the corresponding compounds of formula III are selected from the following structures:

the reaction is preferably carried out under oxygen-free conditions (e.g., the reaction is carried out under an inert gas atmosphere).

The phosphine ligand may be a phosphine ligand conventionally used in the Suzuki reaction in the art.

In some embodiments of the invention, the phosphine ligand is

Tris (2-furanyl) phosphine, diphenyl-2-pyridylphosphine, benzyldiphenylphosphine, diphenylmethylphosphine, tricyclohexylphosphine tetrafluoroborate, bisdiphenylphosphinomethane, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1, 5-bis (diphenylphosphino) pentane, 1, 6-bis (diphenylphosphino) hexane, 2-dicyclohexylphosphine-2 ',6' -dimethoxy-1, 1' -biphenyl

1,1' -bis (diphenylphosphino) ferrocene

2-dicyclohexylphosphine-2 ',4',6 '-triisopropyl-1, 1' -biphenyl

4, 5-bis-diphenylphosphino-9, 9-dimethyloxyHeteroanthracene

And bis (dicyclohexylphosphinophenyl) ether

Wherein R is¹⁰⁰The number of (A) is 0,1, 2, 3, 4 or 5, each R¹⁰⁰Each independently is C_1-4Alkyl (e.g. methyl), C_1-4Alkoxy (e.g., methoxy), fluoro, or trifluoromethyl.

In some embodiments of the invention, the phosphine ligand is triphenylphosphine, tris (2-methoxyphenyl) phosphine, tris (3-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2,4, 6-trimethoxyphenyl) phosphine, tris (4-tolyl) phosphine, tris (3-fluorophenyl) phosphine, tris (4-fluorophenyl) phosphine, tris [4- (trifluoromethyl) phenyl ] phosphine, tris (2, 6-dimethoxyphenyl) phosphine, tris (2-furyl) phosphine, diphenyl-2-pyridylphosphine, benzyldiphenylphosphine, diphenylmethylphosphine, tricyclohexylphosphine tetrafluoroborate, bis-diphenylphosphinomethane, 1, 2-bis (diphenylphosphine) ethane, 1, 3-bis (diphenylphosphine) propane, 1, 4-bis (diphenylphosphine) butane, 1, one or more of 5-bis (diphenylphosphino) pentane, 1, 6-bis (diphenylphosphino) hexane, 2-dicyclohexylphosphine-2 ',6' -dimethoxy-1, 1 '-biphenyl, 1' -bis (diphenylphosphino) ferrocene, 2-dicyclohexylphosphine-2 ',4',6 '-triisopropyl-1, 1' -biphenyl, 4, 5-bis-diphenylphosphino-9, 9-dimethylxanthene and bis (dicyclohexylphosphinophenyl) ether.

In some embodiments of the invention, the phosphine ligand is one or more of tris (2-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tricyclohexylphosphine tetrafluoroborate, 4, 5-bisdiphenylphosphino-9, 9-dimethylxanthene, and bis (dicyclohexylphosphinophenyl) ether.

In some embodiments of the invention, the phosphine ligand is tris (2-methoxyphenyl) phosphine.

The amount of the phosphine ligand may be an amount conventionally used in the art of phosphine ligands in Suzuki reactions.

In some embodiments of the invention, the molar ratio of the phosphine ligand to the compound of formula I is from 1:10 to 1: 20.

The base may be a base conventionally used in the Suzuki reaction in the art, such as an inorganic base.

In some embodiments of the invention, the base is an alkali metal carbonate (e.g., sodium carbonate, potassium carbonate, cesium carbonate), an alkali metal and C_1-4Salts of alkyl-COOH (e.g., salts of alkali metals with acetic acid, salts of alkali metals with pivalic acid, such as sodium acetate, potassium acetate, cesium acetate, salts of alkali metals with pivalic acid, such as sodium pivalate, potassium pivalate, cesium pivalate) and one or more of alkali metal fluorides (e.g., sodium fluoride, potassium fluoride, cesium fluoride).

In some embodiments of the invention, the base is one or more of sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, sodium fluoride, potassium fluoride, cesium fluoride, sodium pivalate, potassium pivalate, and cesium pivalate.

In some embodiments of the invention, the base is cesium with C_1-4Salts of alkyl-COOH.

In some embodiments of the invention, the base is cesium pivalate.

The amount of the base may be that conventionally used in the Suzuki reaction in the art.

In some embodiments of the invention, the molar ratio of the base to the compound of formula I may be from 1:1 to 5:1, for example from 1.5:1 to 2: 1.

The organic solvent may be an organic solvent conventionally used in the Suzuki reaction in the art.

In some embodiments of the invention, the organic solvent is one or more of an ether solvent (e.g., tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethylene glycol dimethyl ether, methyl tert-butyl ether, anisole, diethyl ether), an alkane solvent (e.g., N-hexane), an alcohol solvent (e.g., ethanol), an aromatic hydrocarbon solvent (e.g., toluene), an ester solvent (e.g., ethyl acetate), a halogenated hydrocarbon solvent (e.g., 1, 2-dichloroethane), a nitrile solvent (e.g., acetonitrile), and an amide solvent (e.g., N-dimethylformamide).

In some embodiments of the invention, the organic solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethylene glycol dimethyl ether, methyl tert-butyl ether, anisole, diethyl ether, N-hexane, ethanol, toluene, ethyl acetate, 1, 2-dichloroethane, acetonitrile, and N, N-dimethylformamide.

In some embodiments of the invention, the organic solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, methyl tert-butyl ether, anisole, diethyl ether, N-hexane, ethanol, ethyl acetate, acetonitrile and N, N-dimethylformamide.

In some embodiments of the invention, the organic solvent is tetrahydrofuran.

The amount of the organic solvent to be used may not be particularly limited as long as the reaction is not affected.

The temperature of the reaction may be a reaction temperature conventional in the Suzuki reaction in the art.

In some embodiments of the invention, the temperature of the reaction is from 50 ℃ to 110 ℃, e.g., from 80 ℃ to 110 ℃.

The molar ratio of the compound shown as the formula II to the compound shown as the formula I can be 1:1-10:1, such as 3:1-5: 1.

The palladium catalyst may be a palladium catalyst conventional in the art for the Suzuki reaction, such as tris (dibenzylideneacetone) dipalladium (Pd)₂dba₃) Palladium chloride (PdCl)₂) Bis (triphenylphosphine) palladium dichloride (PdCl)₂(PPh₃)₂) Bis (cyanophenyl) palladium dichloride (PdCl)₂(PhCN)₂) Diallyl palladium dichloride (PdCl)₂(C₃H₅)₂) And palladium bis (acetylacetonate).

In some embodiments of the invention, the palladium catalyst is one or more of tetrakis (triphenylphosphine) palladium, palladium acetate, palladium chloride, bis (triphenylphosphine) palladium dichloride, bis (cyanophenyl) palladium dichloride, diallylpalladium dichloride, and bis (acetylacetonato) palladium.

In some embodiments of the invention, the palladium catalyst is palladium acetate.

The amount of the palladium catalyst may be an amount conventionally used for a palladium catalyst in a Suzuki reaction in the art.

In some embodiments of the invention, the molar ratio of the palladium catalyst to the compound of formula I is from 0.025:1 to 0.20:1, such as from 0.05:1 to 0.1: 1.

The progress of the reaction can be monitored by conventional testing methods in the art (e.g., TLC, HPLC, GC, or NMR), and is generally determined as the end point of the reaction when the compound of formula I is no longer reacted.

The present invention also provides a compound selected from any one of the following structures:

the invention also provides application of the compound as an organic electroluminescent material.

The organic electroluminescent material can be applied to the preparation of deep blue light emitting OLED materials, near infrared emitting OFET materials and the like.

In the present invention, the following terms appearing in the specification and claims have the following meanings, unless otherwise indicated:

in the present invention, the term "substitution" or "substituent" means that one or more hydrogen atoms are replaced by the indicated group. When the substitution position is not indicated, the substitution can be in any position, but the formation of a stable or chemically feasible chemical is only permitted.

In the present invention, the term "optional" or "optionally" means that the subsequently described event or circumstance may, but need not, occur, and that the description includes instances where said event or circumstance occurs and instances where it does not. For example, the term "optionally substituted" means that it may or may not be substituted, and unless otherwise specified, the kind and number of substituents may be arbitrary on the basis that they are chemically realizable.

When any variable (e.g., R) occurs more than one time in the composition or structure of a compound, its definition in each case is independent. Thus, for example, if a group is substituted with 0-2R, the group may optionally be substituted with up to two R, and there are separate options for R in each case. Furthermore, combinations of substituents and/or variants thereof are permissible only if such combinations result in stable compounds.

In the present invention, the term "alkyl" refers to a saturated, straight or branched chain, monovalent hydrocarbon radical having the specified number of carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

In the present invention, the term "alkoxy" refers to an alkyl group attached to the rest of the molecule through an oxygen bridge.

In the present invention, the term "halogen" means fluorine, chlorine, bromine or iodine.

In the present invention, the term "haloalkyl" means an alkyl group in which one or more hydrogen atoms are replaced by halogen, the number of which may be one or more; when the number of the halogen is plural, the halogen may be the same or different. Examples of haloalkyl include, but are not limited to, trifluoromethyl and difluoromethyl.

In the present invention, the term "cycloalkyl" refers to a saturated monovalent cyclic hydrocarbon group having the specified number of ring carbon atoms, and the cycloalkyl group may be monocyclic or polycyclic, and may be a fused ring, spiro ring and bridged ring structure.

In the present invention, the term "cycloalkoxy" refers to a cycloalkyl group attached to the rest of the molecule through an oxygen bridge.

In the present invention, the term "aryl" or "aromatic ring" refers to a monocyclic or polycyclic (e.g., bicyclic or tricyclic) carbocyclic ring of aromatic character. Examples of aryl groups include, but are not limited to, phenyl and naphthyl.

In the present invention, the term "heteroaryl" or "heteroaromatic ring" refers to an aromatic carbocyclic ring containing at least one heteroatom selected from nitrogen, oxygen and sulfur. Examples of heteroaryl groups include, but are not limited to, furyl, thienyl, benzothienyl, benzofuryl, quinolyl, isoquinolyl, isoxazolyl, and pyrazinyl.

The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.

The reagents and starting materials used in the present invention are commercially available.

The positive progress effects of the invention are as follows: provides a brand-new preparation method of polysubstituted ethene compounds. The preparation method of the invention can be suitable for various substrates, and the configuration of double bonds is controllable.

Drawings

FIG. 1 is a single crystal diffractogram of product 3bc of example 12.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

Example 1

Synthesis of compound 3aa:

to a dry Schlenk tube, 3.4mg of Pd (OAc) was added under argon atmosphere₂，10.6mg P(2-OMe-Ph)₃78mg 1aa (0.3mmol), 133mg 2aa (0.9mmol), 141mg CsOPiv, 3mL THF, warmed to 110 ℃ and stirred for 3 h. Quenching the reaction with 5mL of saturated ammonium chloride aqueous solution, extracting with 5mL of ethyl acetate for three times, washing the organic phase with saturated NaCl solution, drying the anhydrous sodium sulfate solid, concentrating, performing column chromatography with n-hexane as eluent, and collecting the product band to obtain 3aaWhite solid 73.0mg, yield 95%.

¹H NMR(400MHz,CDCl₃)δ7.37–7.25(m,8H),7.23–7.18(m,2H),7.16–7.07(m,3H),7.05–6.99(m,2H),6.96(s,1H).

Example 2

Synthesis of compound 3 ab:

starting from 1ab, the procedure is as in example 1, with a yield of 74%.

¹H NMR(400MHz,CDCl₃)δ7.36–7.26(m,5H),7.22(t,J＝7.4Hz,1H),7.17–7.09(m,4H),7.03(dd,J＝13.9,5.5Hz,4H),6.94(s,1H),2.30(s,3H)；EI-MS m/z(％):270(M+).

Example 3

Synthesis of compound 3 ac:

starting from 1ac, the procedure is as in example 1, with a yield of 72%.

¹H NMR(400MHz,CDCl₃)δ7.35–7.26(m,5H),7.17–7.02(m,9H),6.92(s,1H),2.38(s,3H)；EI-MS m/z(％):270(M+).

Example 4

Synthesis of compound 3 ad:

starting from 1ad, the procedure is as in example 1, with a yield of 78%.

¹H NMR(400MHz,CDCl₃)δ7.57(d,J＝8.1Hz,2H),7.38–7.30(m,5H),7.30–7.26(m,2H),7.19–7.12(m,3H),7.05–6.97(m,3H)；EI-MS m/z(％):324(M+).

Example 5

Synthesis of compound 3 ae:

starting with 1ae, the procedure is as in example 1, with a yield of 77%.

¹H NMR(400MHz,CDCl₃)δ7.36–7.27(m,5H),7.19–7.09(m,5H),7.08–7.04(m,2H),6.90(s,1H),6.89–6.86(m,1H),6.86–6.83(m,1H),3.83(s,3H)；EI-MS m/z(％):286(M+).

Example 6

Synthesis of compound 3 af:

starting from 1af, the procedure is described in example 1 with a yield of 85%.

¹H NMR(400MHz,CDCl₃)δ7.33–7.28(m,5H),7.16(ddd,J＝15.1,9.4,5.0Hz,5H),7.02(dd,J＝12.1,5.3Hz,4H),6.96(s,1H)；EI-MS m/z(％):274(M+).

Example 7

Synthesis of Compound 3 ag:

starting with 1ag, the procedure is described in example 1 with a yield of 85%.

¹H NMR(400MHz,CDCl₃)δ7.35–7.26(m,7H),7.20–7.10(m,5H),7.07–7.01(m,2H),6.96(s,1H)；EI-MS m/z(％):290(M+).

Example 8

Synthesis of compound 3 ah:

starting from 1ah, the procedure is as in example 1, 91% yield.

¹H NMR(400MHz,CDCl₃)δ8.57(d,J＝5.9Hz,2H),7.33(t,J＝5.7Hz,3H),7.30–7.23(m,4H),7.20–7.12(m,5H),7.04(dd,J＝6.8,2.6Hz,3H)；EI-MS m/z(％):257(M+)；HRMS(ESI):m/z C19H16N[M+H]⁺Calculated value 258.1277, found value 258.1277.

Example 9

Synthesis of compound 3 ai:

starting from 1ai, the procedure is as in example 1, with a yield of 40%.

¹H NMR(400MHz,CDCl₃)δ7.85(d,J＝7.7Hz,1H),7.79(d,J＝8.4Hz,1H),7.75–7.66(m,2H),7.52–7.42(m,2H),7.32(tt,J＝4.9,3.1Hz,6H),7.06(d,J＝13.6Hz,6H).¹³C NMR(101MHz,CDCl₃)δ143.78,142.56,138.10,137.43,133.77,132.86,129.72,129.47,128.83,128.75,128.37,128.29,128.24,128.17,127.95,127.86,127.71,126.97,126.16,126.12.

Example 10

Synthesis of Compound 3 ba:

see example 1 for operation with 97% yield starting from 1 ba.

¹H NMR(400MHz,CDCl₃)δ7.28(dd,J＝6.8,2.0Hz,1H),7.25–7.09(m,13H),6.61(s,1H),2.11(s,3H)；EI-MS m/z(％):270(M+).

Example 11

Synthesis of compound 3 bb:

starting from 1bb, the procedure is as in example 1, 69% yield.

¹H NMR(400MHz,CDCl₃)δ7.34(dd,J＝5.0,1.7Hz,3H),7.25–7.19(m,3H),7.18–7.09(m,6H),7.06–7.00(m,2H),6.96(s,1H),2.35(s,3H)；EI-MS m/z(％):270(M+).

Example 12

Synthesis of compound 3 bc:

starting from 1bc, the procedure is described in example 1, with a yield of 60%. 20mg of 3bc was dissolved in 0.2mL of methylene chloride at 50 ℃ and allowed to stand at-20 ℃. After 24h, white needle-like crystals precipitated, which were filtered off and subjected to single crystal diffraction tests. The single crystal diffractogram is shown in FIG. 1.

¹H NMR(400MHz,CDCl₃)δ7.30(s,3H),7.21(d,J＝7.4Hz,4H),7.11(d,J＝8.7Hz,5H),7.01(d,J＝6.6Hz,2H),6.93(s,1H),2.34(s,3H)；EI-MS m/z(％):270(M+).

Example 13

Synthesis of compound 3 bd:

starting from 1bd, the procedure is described in example 1 with a yield of 68%.

¹H NMR(400MHz,CDCl₃)δ7.28(dd,J＝17.9,11.4Hz,5H),7.15(d,J＝29.4Hz,5H),7.07–6.94(m,4H),6.90(s,1H)；EI-MS m/z(％):274(M+).

Example 14

Synthesis of compound 3 be:

starting from 1be, the procedure is as in example 1, with a yield of 90%.

¹H NMR(400MHz,CDCl₃)δ7.33(dd,J＝4.9,1.6Hz,3H),7.29–7.21(m,4H),7.18(dd,J＝6.6,3.0Hz,2H),7.15–7.08(m,3H),7.01(dd,J＝7.4,2.0Hz,2H),6.94(s,1H)；EI-MS m/z(％):290(M+).

Example 15

Synthesis of compound 3 bf:

starting from 1bf, the procedure is as in example 1, with a yield of 79%.

¹H NMR(400MHz,CDCl₃)δ7.56(d,J＝8.3Hz,2H),7.42(d,J＝8.2Hz,2H),7.38–7.32(m,3H),7.21–7.18(m,2H),7.15(dd,J＝5.2,1.9Hz,3H),7.04(dd,J＝7.0,2.6Hz,2H),7.01(s,1H)；EI-MS m/z(％):324(M+).

Example 16

Synthesis of compound 3 bg:

starting from 1bg, the procedure is described in example 1, with a yield of 70%.

¹H NMR(400MHz,CDCl₃)δ7.36–7.29(m,3H),7.29–7.23(m,2H),7.23–7.17(m,2H),7.15–7.06(m,3H),7.04–6.97(m,2H),6.89(s,1H),6.87–6.82(m,2H),3.81(s,3H)；EI-MS m/z(％):324(M+).

Example 17

Synthesis of compound 3 bh:

starting from 1bh, the procedure is as in example 1, 67% yield.

¹H NMR(400MHz,CDCl₃)δ7.38(dd,J＝5.1,1.6Hz,3H),7.30(dd,J＝6.6,2.8Hz,2H),7.21(d,J＝5.1Hz,1H),7.09(t,J＝5.8Hz,3H),7.05(s,1H),6.99–6.90(m,3H),6.72(d,J＝3.5Hz,1H).¹³C NMR(101MHz,CDCl₃)δ147.91,139.39,136.59,136.23,129.87,129.41,128.78,127.98,127.83,127.45,126.80,126.31,126.08,124.71；EI-MS m/z(％):262(M+)；HRMS(ESI):m/z C18H14S[M+H]⁺Calculated 262.0816, found 262.0821.

Example 18

Synthesis of Compound 3 bi:

starting from 1bi, the procedure is described in example 1, with a yield of 71%.

¹H NMR(400MHz,CDCl₃)δ7.86–7.72(m,3H),7.70(s,1H),7.52(dd,J＝8.6,1.8Hz,1H),7.48–7.41(m,2H),7.39–7.33(m,3H),7.30–7.22(m,3H),7.13(dd,J＝13.2,5.5Hz,4H),7.09–7.02(m,2H).¹³C NMR(101MHz,CDCl₃)δ142.54,140.77,140.29,137.38,133.28,132.80,130.48,129.58,128.69,128.24,127.98,127.70,127.52,127.51,126.83,126.79,126.15,125.96,125.59；EI-MS m/z(％):306(M+)；HRMS(ESI):m/z C24H18[M+H]⁺Calculated value 306.1409, found value 306.1402.

Example 19

Synthesis of compound 3 bj:

starting from 1bj, the procedure is as in example 1, with a yield of 94%.

¹H NMR(400MHz,CDCl₃)δ8.10(d,J＝8.4Hz,1H),7.83(dd,J＝16.2,7.9Hz,2H),7.45(ddd,J＝10.9,9.6,7.0Hz,3H),7.41–7.33(m,1H),7.29–7.13(m,10H),6.80(s,1H)；EI-MS m/z(％):306(M+).

Example 20

Synthesis of compound 3 bk:

starting from 1bk, the procedure is as in example 1, with a yield of 88%.

¹H NMR(400MHz,CDCl₃)δ7.39–7.21(m,4H),7.16–7.08(m,2H),7.08–6.98(m,3H),6.85(d,J＝6.5Hz,2H),6.40(s,1H),3.12–2.44(m,1H),1.11(d,J＝6.8Hz,6H).¹³C NMR(101MHz,CDCl₃)δ149.56,141.36,137.74,129.12,128.49,127.89,126.82,126.11,124.30,37.52,21.92.

Example 21

Synthesis of compound 3 bl:

starting from 1bl, the procedure is described in example 1 with a yield of 88%.

¹H NMR(400MHz,CDCl₃)δ7.41–7.32(m,6H),7.31–7.19(m,3H),7.16(d,J＝7.3Hz,2H)；EI-MS m/z(％):205(M+).

Example 22

Synthesis of compound 3 bm:

starting from 1bm, the procedure is described in example 1, with a yield of 81%.

¹H NMR(400MHz,CDCl₃)δ7.85(s,1H),7.41–7.34(m,3H),7.24–7.10(m,5H),7.03(d,J＝7.2Hz,2H),3.79(s,3H).

Example 23

Synthesis of Compound 3 ca:

starting from 2ca, the procedure is described in example 1, with a yield of 76%.

¹H NMR(400MHz,CDCl₃)δ7.38(s,1H),7.37–7.28(m,9H),7.21–7.15(m,2H),7.10(d,J＝8.2Hz,2H),6.97(s,1H)；EI-MS m/z(％):324(M+).

Example 24

Synthesis of compound 3 cb:

starting from 2cb, the procedure is as in example 1, with a yield of 81%.

¹H NMR(400MHz,CDCl₃)δ7.38–7.26(m,8H),7.18(dd,J＝7.0,2.6Hz,2H),6.98(dd,J＝8.6,5.6Hz,2H),6.92(s,1H),6.81(t,J＝8.7Hz,2H)；EI-MS m/z(％):274(M+).

Example 25

Synthesis of compound 3 cc:

starting from 2cc, the procedure is as in example 1, with a yield of 76%.

¹H NMR(400MHz，CDCl₃)δ7.38–7.27(m，8H)，7.18(dd，J＝6.6，3.0Hz2H),7.09(d,J＝8.5Hz,2H),6.95(s,1H),6.92(s,1H),6.90(s,1H)；EI-MS m/z(％):290(M+).

Example 26

Synthesis of compound 3 cd:

starting from 2cd, the procedure is as in example 1, with a yield of 72%.

¹H NMR(400MHz,CDCl₃)δ7.36–7.27(m,7H),7.23(ddd,J＝9.3,6.6,1.8Hz,3H),6.95(d,J＝8.7Hz,2H),6.91(s,1H),6.67(d,J＝8.8Hz,2H),3.74(s,3H)；EI-MS m/z(％):286(M+).

Example 27

Synthesis of Compound 3 ce:

starting from 2ce, the procedure is described in example 1, yield 79%.

¹H NMR(400MHz,CDCl₃)δ7.37–7.26(m,8H),7.23–7.18(m,2H),6.97–6.88(m,5H),2.26(s,3H)；EI-MS m/z(％):270(M+).

Example 28

Synthesis of compound 3 cf:

starting from 2cf, the procedure is as in example 1, with a yield of 60%.

¹H NMR(400MHz,CDCl₃)δ7.38–7.28(m,5H),7.23–7.18(m,3H),7.15–7.07(m,3H),7.06–7.00(m,1H),6.97(s,1H),6.90–6.79(m,2H),2.33(s,3H)；EI-MS m/z(％):270(M+).

Example 29

Synthesis of compound 3 cg:

starting from 2cg, the procedure is as in example 1, with a yield of 44%.

¹H NMR(400MHz,CDCl₃)δ7.43–7.31(m,5H),7.18–7.08(m,3H),7.07–6.99(m,1H),6.99–6.90(m,4H),6.83(s,1H),2.12(s,6H).¹³C NMR(101MHz,CDCl₃)δ144.31,143.41,140.20,136.86,136.13,129.74,128.40,128.13,127.66,127.50,127.40,127.20,127.15,126.69,20.55；EI-MS m/z(％):284(M+)；HRMS(ESI):m/z C20H17N[M+H]⁺Calculated value 284.1565, found value 284.1572.

Example 30

Synthesis of Compound 3 ch:

starting from 2ch, the procedure is described in example 1 with a yield of 83%.

¹H NMR(400MHz,CDCl₃)δ7.39(d,J＝8.3Hz,2H),7.37–7.30(m,8H),7.17(s,2H),7.08(d,J＝8.4Hz,2H),6.94(s,1H)；EI-MS m/z(％):281(M+).

Example 31

Synthesis of compound 3 ci:

starting from 2ci, the procedure is as in example 1, with a yield of 74%.

¹H NMR(400MHz,CDCl₃)δ7.98(d,J＝8.8Hz,2H),7.40–7.30(m,8H),7.17(dd,J＝7.1,2.3Hz,2H),7.13(d,J＝8.8Hz,2H),7.00(s,1H)；EI-MS m/z(％):301(M+).

Example 32

Synthesis of compound 3 cj:

starting from 2cj, the procedure is as in example 1, with a yield of 74%.

¹H NMR(400MHz,CDCl₃)δ7.31(dd,J＝6.7,2.8Hz,8H),7.22–7.16(m,4H),7.04(d,J＝8.1Hz,2H),6.95(s,1H),3.01(s,6H).¹³C NMR(101MHz,CDCl₃)δ171.57,144.01,143.26,140.11,138.93,134.29,130.45,129.49,128.86,128.38,127.90,127.80,127.77,127.36,127.09.

Example 33

Synthesis of Compound 3 ck:

starting from 2ck, the procedure is described in example 1, with a yield of 63%.

¹H NMR(400MHz,CDCl₃)δ7.37–7.27(m,8H),7.23–7.19(m,2H),6.93(t,J＝7.8Hz,1H),6.88(s,1H),6.45(d,J＝7.8Hz,2H),6.33(s,1H),3.43(s,2H)；EI-MS m/z(％):271(M+)；HRMS(ESI):m/z C20H17N[M+H]⁺Calculated 271.1361, found 271.1362.

Example 34

Synthesis of compound 3 cl:

starting from 2cl, the procedure is described in example 1 with a yield of 76%.

¹H NMR(400MHz,CDCl₃)δ7.38–7.25(m,10H),7.25–7.19(m,2H),7.00(d,J＝7.9Hz,2H),6.95(s,1H),0.21(s,9H).¹³C NMR(101MHz,CDCl₃)δ143.56,142.81,140.59,139.19,137.77,133.16,130.42,128.90,128.85,128.33,128.29,127.70,127.64,127.57,-1.01.

Example 35

Synthesis of Compound 3 cm:

starting from 2cm, the procedure is described in example 1 with a yield of 77%.

¹H NMR(400MHz,CDCl₃)δ9.89(s,1H),7.64(d,J＝8.2Hz,2H),7.40–7.29(m,8H),7.22–7.10(m,4H),7.00(s,1H).¹³C NMR(101MHz,CDCl₃)δ191.83,146.06,143.95,142.87,139.79,134.48,130.37,130.10,129.57,128.95,128.46,128.32,128.11,127.94,126.96；EI-MS m/z(％):284(M+)；HRMS(ESI):m/z C21H16O[M+H]⁺Calculated value 284.1201, found value 284.1207.

Example 36

Synthesis of compound 3 cn:

starting from 2cn, the procedure is as in example 1, 84% yield.

¹H NMR(400MHz,CDCl₃)δ7.72(d,J＝8.4Hz,2H),7.38–7.29(m,8H),7.19(dd,J＝6.5,2.9Hz,2H),7.09(d,J＝8.3Hz,2H),6.99(s,1H),2.53(s,3H).¹³C NMR(101MHz,CDCl₃)δ197.73,145.36,142.98,142.47,139.94,135.11,130.38,129.70,128.92,128.43,128.21,128.18,127.98,127.88,127.08,26.69；EI-MS m/z(％):298(M+)；HRMS(ESI):m/z C22H18O[M+H]⁺Calculated value 298.1358, found value 298.1364.

Example 37

Synthesis of compound 3 co:

starting from 2co, the procedure is described in example 1 with a yield of 65%.

¹H NMR(400MHz,CDCl₃)δ7.79(d,J＝8.4Hz,2H),7.33(d,J＝5.2Hz,8H),7.18(dd,J＝6.6,3.0Hz,2H),7.07(d,J＝8.3Hz,2H),6.98(s,1H),3.86(s,3H).¹³C NMR(101MHz,CDCl₃)δ166.88,145.00,142.89,142.12,139.78,130.26,129.38,129.22,128.73,128.27,127.97,127.92,127.78,127.74,127.05,51.99；EI-MS m/z(％):314(M+)；HRMS(ESI):m/z C22H18O2[M+H]⁺Calculated 314.1307, found 314.1310.

Example 38

Synthesis of Compound 3 cp:

starting from 2cp, the procedure is described in example 1, 81% yield.

¹H NMR(400MHz,CDCl₃)δ7.37–7.26(m,3H),7.20(dd,J＝7.1,2.1Hz,1H),7.00(d,J＝8.4Hz,1H),6.96–6.88(m,1H),2.41(s,1H)；EI-MS m/z(％):302(M+).

Example 39

Synthesis of compound 3 cq:

starting from 2cq, the procedure is as in example 1, with a yield of 99%.

¹H NMR(400MHz,CDCl₃)δ7.68(d,J＝8.5Hz,2H),7.40–7.31(m,8H),7.21–7.13(m,4H),6.98(s,1H),3.01(s,3H).¹³C NMR(101MHz,CDCl₃)δ146.43,143.15,142.54,139.41,137.94,130.20,130.19,129.00,128.43,128.39,128.18,127.85,127.08,125.99,44.51；EI-MS m/z(％):334(M+)；

Example 40

Synthesis of Compound 3 da:

starting from 2da, the procedure is as in example 1, with a yield of 66%.

¹H NMR(400MHz,CDCl₃)δ7.46–7.38(m,3H),7.34–7.28(m,4H),7.28–7.23(m,4H),7.14(d,J＝3.4Hz,2H),6.88(s,1H),5.61(d,J＝1.1Hz,1H).¹³C NMR(101MHz,CDCl₃)δ142.61,142.56,142.31,141.01,140.76,130.04,128.97,128.36,127.71,127.34,126.98,123.56,117.69,110.18.

EXAMPLE 41

Synthesis of Compound 3 db:

starting from 2db, the procedure is described in example 1, with a yield of 76%.

¹H NMR(400MHz,CDCl₃)δ7.51–7.44(m,3H),7.37–7.27(m,7H),7.27–7.23(m,2H),7.04(d,J＝5.0Hz,1H),6.93(d,J＝3.2Hz,1H),6.87(dd,J＝5.0,3.7Hz,1H)；EI-MS m/z(％):262(M+)；HRMS(ESI):m/z C18H14S[M+H]⁺Calculated value 262.0816, found value 262.0822.

Example 42

Synthesis of Compound 3 dc:

starting from 2dc, the procedure is described in example 1 with a yield of 87%.

¹H NMR(400MHz,CDCl₃)δ8.90(s,1H),8.32(s,2H),7.42–7.30(m,8H),7.18(dd,J＝6.5,3.0Hz,2H),6.83(s,1H).¹³C NMR(101MHz,CDCl₃)δ156.77,156.04,147.42,141.90,138.89,131.57,129.92,129.33,128.61,128.52,128.50,127.71,120.24.

Example 43

Synthesis of Compound 3 dd:

starting from 2dd, the procedure is described in example 1 with a yield of 70%.

¹H NMR(400MHz,CDCl₃)δ8.36(d,J＝1.8Hz,1H),8.32(dd,J＝4.7,1.3Hz,1H),7.39–7.29(m,8H),7.21–7.14(m,3H),7.01(dd,J＝7.9,4.8Hz,1H),6.93(s,1H)；EI-MS m/z(％):256(M-H)^-.

Example 44

Synthesis of Compound 3 de:

starting from 2de, the procedure is described in example 1 with a yield of 65%.

¹H NMR(400MHz,CDCl₃)δ7.54–7.37(m,3H),7.37–7.15(m,7H),7.02(s,1H),6.89(s,1H),6.57(s,1H),3.72(s,3H)；EI-MS m/z(％):260(M+)；HRMS(ESI):m/z C18H17N2[M+H]⁺Calculated value 261.1386, found value 261.1386.

Example 45

Synthesis of compound 3 df:

starting from 2df, the procedure is as in example 1, with a yield of 97%.

¹H NMR(400MHz,CDCl₃)δ8.59(d,J＝2.1Hz,1H),8.03(d,J＝8.4Hz,1H),7.69(d,J＝1.9Hz,1H),7.62(ddd,J＝8.4,6.8,1.4Hz,1H),7.54(d,J＝8.1Hz,1H),7.50–7.42(m,1H),7.41–7.30(m,8H),7.28–7.19(m,3H),7.10(s,1H)；EI-MS m/z(％):307(M+)；HRMS(ESI):m/z C23H18N[M+H]⁺Calculated 308.1434, found 308.1433.

Example 46

Synthesis of compound 3 dg:

starting from 2dg, the procedure is as in example 1, with a yield of 63%.

¹H NMR(400MHz,CDCl₃)δ7.47(q,J＝5.0Hz,3H),7.37(dd,J＝7.9,1.3Hz,2H),7.31(dt,J＝8.2,5.4Hz,7H),7.19(t,J＝7.7Hz,1H),7.11(t,J＝7.4Hz,1H),7.07(s,1H),5.80(s,1H).¹³C NMR(101MHz,CDCl₃)δ154.96,154.10,144.13,141.57,140.11,129.68,129.09,129.05,128.51,128.16,128.08,127.31,124.40,122.83,120.95,116.29,110.93,105.36；EI-MS m/z(％):296(M+)；HRMS(ESI):m/z C22H17O[M+H]⁺Calculated value 297.1274, found value 297.1274.

Example 47

Synthesis of compound 3 dh:

starting from 2dh, the procedure is as in example 1, 93% yield.

¹H NMR(400MHz,CDCl₃)δ8.15(dd,J＝6.2,3.4Hz,1H),7.82(dt,J＝6.8,3.6Hz,1H),7.64(d,J＝8.1Hz,1H),7.51–7.44(m,3H),7.42(dd,J＝7.9,1.6Hz,2H),7.39–7.30(m,3H),7.19–7.11(m,4H),7.08(dd,J＝7.7,1.8Hz,2H),7.04(d,J＝7.2Hz,1H)；EI-MS m/z(％):306(M+).

Example 48

Synthesis of Compound 3 di:

starting from 2di, the procedure is as in example 1, 53% yield.

¹H NMR(400MHz,CDCl₃)δ7.70(dd,J＝6.0,3.4Hz,1H),7.63(dd,J＝6.0,3.3Hz,1H),7.57(s,1H),7.53(d,J＝8.6Hz,1H),7.44–7.29(m,9H),7.27–7.21(m,3H),7.13(s,1H),7.05(dd,J＝8.6,1.4Hz,1H)；EI-MS m/z(％):306(M+)。

Example 49:

starting from 2dj, the procedure is as in example 1, with a yield of 67%.

¹H NMR(400MHz,Tol)δ8.27–8.17(m,2H),8.05(s,1H),7.75–7.66(m,2H),7.52–7.43(m,3H),7.26–7.13(m,7H),6.97–6.89(m,2H),6.63–6.52(m,3H)；¹³C NMR(100MHz,Tol)δ147.69,143.41,140.30,132.99,131.88,130.03,129.94,129.00,128.78,128.61,128.07,127.82,127.32,126.95,126.64,125.62,125.26,125.23。

EI-MS(m/z,％)::356(M⁺,100),278(44.53),279(35.6),276(31.8)；HRMS(EI):m/z C₂₈H₂₀[M]⁺Calculated 356.1565, found 356.1567.

Example 50

Starting from 2dj, the procedure is as in example 1, 67% yield.

Example 51: investigating different arylboron compounds

In a dry Schlenk tube, 2.3mg of Pd (OAc) were added under argon atmosphere₂，7.1mg P(2-OMe-Ph)₃52mg of 1aa (0.2mmol), the arylboron compound shown below (0.6mmol), 77mg of CsOAc, 2mL of THF, were heated to 110 ℃ and stirred for 3 h. 10mL of dichloromethane was added for dilution, 25. mu.L of dodecane internal standard was added, and the yield and ratio were determined by GC-FID (320 ℃ gassed injection, initial temperature 50 ℃, 15 ℃ per minute increase, 10 minutes after 300 ℃ increase).

The percentages are yields of compound 3aa, and the ratio in parentheses is the 3aa to 4aa yield ratio.

Various types of boronic acid groups are suitable for use in this reaction.

Example 52: investigating different phosphine ligands

In a dry Schlenk tube, 2.3mg of Pd (OAc) were added under argon atmosphere₂5 mol% or 10 mol% of ligand (for monophosphine ligands, e.g. L)_1-15、L_22-23Using 10 mol% for bisphosphine ligands, e.g. L_16-21、L_24-265 mol%), 52mg 1aa (0.2mmol), 2aa (0.6mmol), 77mg CsOAc, 2mL THF were used, warmed to 110 ℃ and stirred for 3 h. 10mL of dichloromethane was added for dilution, 25. mu.L of dodecane internal standard was added, and the yield and ratio were determined by GC-FID.

Various types of phosphine ligands are suitable for use in the present invention.

Example 53: investigating different solvents

Dried Schlenk tube, 2.3mg Pd (OAc) was added under argon atmosphere₂，7.1mg P(2-OMe-Ph)₃52mg of 1aa (0.2mmol), 2aa (0.3mmol), 77mg of CsOAc, 2mL of the solvents mentioned in the table below, are stirred at 110 ℃ for 3 h. 10mL of dichloromethane was added for dilution, 25. mu.L of dodecane internal standard was added, and the yield and ratio were determined by GC-FID.

Various types of solvents are suitable for this reaction.

Example 54: investigating different palladium sources

Dried Schlenk tube, under argon, was charged with 5 mol% of a palladium source shown in the following Table, 7.1mg of P (2-OMe-Ph)₃52mg of 1aa (0.2mmol), 2aa (0.3mmol), 77mg of CsOAc, 2mL of THF, warm to 110 ℃ and stir for 3 h. 10mL of dichloromethane was added for dilution, 25. mu.L of dodecane internal standard was added, and the yield and ratio were determined by GC-FID.

Various types of palladium sources are suitable for this reaction.

Example 55: investigating different bases

Dried Schlenk tube, 2.3mg Pd (OAc) was added under argon atmosphere₂，7.1mg P(2-OMe-Ph)₃52mg of 1aa (0.2mmol), 2aa (0.6mmol), a base as shown in the following table, 2mL of THF, was heated to 110 ℃ and stirred for 3 h. 10mL of dichloromethane was added for dilution, 25. mu.L of dodecane internal standard was added, and the yield and ratio were determined by GC-FID.

Various types of bases are suitable for this reaction, among which the alkali metal salts of organic acids work better.

Example 56: investigating boron ester equivalent

Dried Schlenk tube, 2.3mg Pd (OAc) was added under argon atmosphere₂，7.1mg P(2-OMe-Ph)₃52mg of 1aa (0.2mmol), 2aa equivalents as shown in the table below, 94mg of CsOPiv, 2mL of THF, were heated to 110 ℃ and stirred for 3 h. 10mL of dichloromethane was added for dilution, 25. mu.L of dodecane internal standard was added, and the yield and ratio were determined by GC-FID.

Example 57: investigation of reaction temperature

Dried Schlenk tube, 2.3mg Pd (OAc) was added under argon atmosphere₂，7.1mg P(2-OMe-Ph)₃52mg of 1aa (0.2mmol), 2aa (0.6mmol), 94mg of CsOPiv, 2mL of THF, were heated to the temperature indicated in the following table and stirred for 3 h. 10mL of dichloromethane was added for dilution, 25. mu.L of dodecane internal standard was added, and the yield and ratio were determined by GC-FID.

Example 58

In a dry Schlenk tube, 1.67g of boric acid (10mmol), 0.56mL of ethylene glycol (11mmol), 1.80g of anhydrous magnesium sulfate (15mmol), 50mL of dry dichloromethane were added under argon atmosphere, and the mixture was stirred at room temperature for 4 h. The solid was filtered off with suction, the filtrate was retained, the solvent was removed by rotation and dried in vacuo to give 1.57g of an off-white solid in 81% yield.

¹H NMR(400MHz,CDCl₃)δ8.22(d,J＝8.6Hz,2H),7.98(d,J＝8.5Hz,2H),4.44(s,4H).

Example 59

See example 58 for operation with 86% yield.

¹H NMR(400MHz,CDCl₃)δ7.84(d,J＝8.0Hz,2H),7.42(d,J＝8.1Hz,2H),4.39(s,4H),3.11(s,3H),2.95(s,3H).

Example 60

See example 58 for operation in 90% yield.

¹H NMR(400MHz,CDCl₃)δ7.78(d,J＝7.7Hz,2H),7.55(d,J＝7.8Hz,2H),4.38(s,4H),0.27(s,9H).

Example 61

See example 58 for operation in 87% yield.

¹H NMR(400MHz,CDCl₃)δ7.92(ddd,J＝13.4,7.8,3.6Hz,4H),4.40(s,4H),2.61(d,J＝2.4Hz,3H).

Example 62

See example 58 for operation in 72% yield.

¹H NMR(400MHz,CDCl₃)δ7.71(d,J＝8.2Hz,1H),7.36–7.09(m,4H),4.37(s,4H),2.50(s,3H).

Example 63

See example 58 for operation in 97% yield.

¹H NMR(400MHz,CDCl₃)δ7.97(dd,J＝23.0,8.2Hz,4H),4.43(s,4H),3.07(s,3H).

Example 64

See example 58 for operation in 75% yield.

¹H NMR(400MHz,CDCl₃)δ8.50(s,1H),8.44(d,J＝8.6Hz,2H),8.00(d,J＝7.8Hz,2H),7.55–7.39(m,4H),4.63(s,4H)；¹³C NMR(100MHz,CDCl₃)δ136.03,131.12,129.88,128.79,128.57,125.83,124.96,66.11.

Example 65

See example 58 for operation in 50% yield.

¹H NMR(400MHz,CDCl₃)δ9.05(d,J＝9.2Hz,1H),8.56(d,J＝7.7Hz,1H),8.27–8.10(m,5H),8.07(d,J＝8.9Hz,1H),8.01(t,J＝7.6Hz,1H),4.56(s,4H)；¹³C NMR(101MHz,cdcl₃)δ136.47,134.08,133.64,131.07,130.69,128.71,127.90,127.79,127.43,125.76,125.45,125.32,124.54,124.39,124.13,66.05。

Effect example 1

(1) Preparation of compound mother liquor:

weighing 0.01mmol of compound, dissolving in 1mL of chromatographic pure THF, and mixing well by ultrasonic oscillation to obtain 10^-2mmol solution; taking 100 μ L of the above solution with a pipette, adding 900 μ L of chromatographically pure THF, dissolving, and ultrasonic vibratingGo to obtain 10^-3mmol solution; taking 40 μ L of the above solution with a pipette, adding 3mL +960 μ L of chromatographically pure THF, dissolving, and ultrasonic oscillating to obtain 10^-5mmol of the solution.

(2) Determination of the maximum absorption wavelength of a Compound

2mL of the solution prepared in step (1) was taken, and the maximum absorption peak of each compound was measured by an ultraviolet/visible spectrometer (Shimadzu UV-2600spectrophotometer) at 25 ℃.

(3) Measurement of Absolute Quantum efficiency of Compound (solution State)

Taking 2mL of the solution prepared in the step (1), testing the solution in an absolute quantum efficiency tester (Hamamatsu absolute PL quaternary yield quantum meter C11347Quantaurus _ QY) at 25 ℃, setting the excitation wavelength as the maximum absorption wavelength of each compound respectively, and determining the absolute quantum efficiency.

(4) Determination of the Absolute Quantum efficiency of Compounds (solid State)

2mg of the compound was measured at 25 ℃ in an absolute quantum efficiency tester (Hamamatsu absolute PL quaternary yield quantum meter C11347Quantaurus _ QY), and the excitation wavelength was set to the maximum absorption wavelength of each compound, respectively, to measure the absolute quantum efficiency.

Claims

1. A preparation method of polysubstituted ethylene compounds shown as a formula III comprises the following steps: under the oxygen-free condition, in an organic solvent, carrying out the following reaction on a compound shown as a formula I and a compound shown as a formula II in the presence of a palladium catalyst, a phosphine ligand and alkali to obtain a polysubstituted ethylene compound shown as a formula III;

wherein ring A is C_6-16An aromatic or 5-16 membered heteroaromatic ring;

each R³Independently of one another is fluorine, chlorine, cyano, C_1-6Alkyl radical, C_3-6Cycloalkyl radical, C_1-6Alkoxy radical, C_3-6Cycloalkoxy or C_1-6A haloalkyl group;

m is 0,1, 2, 3 or 4;

x is Br, I or OTf;

R¹is C_1-6Alkyl, cyano, or,

C_6-16Aryl or 5-16 membered heteroaryl, said C_6-16Aryl or 5-16 membered heteroaryl optionally substituted with one or more R^1-1Substituted in which each R^1-1Each independently of the others being fluorine, chlorine, cyano, C_1-6Alkyl radical, C_3-6Cycloalkyl, C_1-6Alkoxy radical, C_3-6Cycloalkoxy or C_1-6A haloalkyl group;

R⁶is C_1-6An alkyl group;

ring B is C_6-16An aromatic or 5-16 membered heteroaromatic ring;

each R⁵Each independently of the other is fluorine, chlorine, C_1-6Alkyl radical, C_3-6Cycloalkyl radical, C_1-6Alkoxy radical, C_3-6Cycloalkoxy, cyano, nitro, aldehyde, amino,

Or C_1-6A haloalkyl group; wherein R is^2-2、R^2-3、R^2-4、R^2-5、R^2-6、R^2-7、R^2-8、R^2-9、R^2-10And R^2-11Each independently is C_1-6An alkyl group;

n is 0,1, 2, 3 or 4;

R⁴is composed of

the heteroatoms in the heteroaromatic ring or heteroaryl group are each independently nitrogen, oxygen or sulfur, and the number of heteroatoms is independently 1,2, 3 or 4;

the base is alkali metal carbonate, alkali metal and C_1-4One or more of a salt of alkyl-COOH and an alkali metal fluoride.

2. The method of claim 1, wherein: at R³、R¹、R⁶、R⁵、R^1-1、R^2-2、R^2-3、R^2-4、R^2-5、R^2-6、R^2-7、R^2-8、R^2-9、R^2-10、R^2-11、R⁵¹、R⁵²、R⁵³、R⁵⁴、R⁵⁵、R⁵⁶、R⁵⁷、R⁵⁸、R⁵⁹、R⁶⁰、R⁶¹And R⁶²In (b), the C_1-6Each alkyl group is independently C_1-4An alkyl group;

and/or, at R³、R⁵And R^1-1In (b), the C_1-6Alkoxy is each independently C_1-4An alkoxy group;

and/or, at R³、R⁵And R^1-1In (b), the C_1-6Haloalkyl is each independently C_1-4A haloalkyl group;

and/or, at R³、R⁵And R^1-1In (b), the C_1-6Halogen in haloalkyl is fluorine；

And/or, when ring A is C_6-16When it is an aromatic ring, said C_6-16The aromatic ring being C_6-14An aromatic ring;

and/or, when ring a is a 5-16 membered heteroaryl ring, said 5-16 membered heteroaryl ring is a 5-10 membered heteroaryl ring;

and/or when R¹Is C_6-16Aryl is said to C_6-16Aryl is C_6-14An aryl group;

and/or when R¹When it is a 5-16 membered heteroaryl group, said 5-16 membered heteroaryl group is a 5-10 membered heteroaryl group;

and/or, when ring B is a 5-16 membered heteroaryl ring, the 5-16 membered heteroaryl ring is a 5-10 membered heteroaryl ring;

and/or the phosphine ligand is

One or more of tris (2-furanyl) phosphine, diphenyl-2-pyridylphosphine, benzyldiphenylphosphine, diphenylmethylphosphine, tricyclohexylphosphine tetrafluoroborate, bisdiphenylphosphinomethane, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1, 5-bis (diphenylphosphino) pentane, 1, 6-bis (diphenylphosphino) hexane, 2-dicyclohexylphosphine-2 ',6' -dimethoxy-1, 1 '-biphenyl, 1' -bis (diphenylphosphino) ferrocene, 2-dicyclohexylphosphine-2 ',4',6 '-triisopropyl-1, 1' -biphenyl, 4, 5-bisdiphenylphosphino-9, 9-dimethylxanthene and bis (dicyclohexylphosphinophenyl) ether, wherein R is¹⁰⁰Is 0,1, 2, 3, 4 or 5, each R¹⁰⁰Each independently is C_1-4Alkyl radical, C_1-4Alkoxy, fluoro or trifluoromethyl;

and/or the molar ratio of the phosphine ligand to the compound shown in the formula I is 1:10-1: 20;

and/or the molar ratio of the alkali to the compound shown in the formula I is 1:1-5: 1;

and/or the organic solvent is one or more of an ether solvent, an alkane solvent, an alcohol solvent, an aromatic hydrocarbon solvent, an ester solvent, a halogenated hydrocarbon solvent, a nitrile solvent and an amide solvent;

and/or the temperature of the reaction is 50-110 ℃;

and/or the molar ratio of the compound shown in the formula II to the compound shown in the formula I is 1:1-10: 1;

and/or the palladium catalyst is one or more of tris (dibenzylideneacetone) dipalladium, palladium chloride, bis (triphenylphosphine) palladium dichloride, bis (cyanobenzene) palladium dichloride, diallyl palladium dichloride and bis (acetylacetonato) palladium;

and/or the molar ratio of the palladium catalyst to the compound shown in the formula I is 0.025-0.20: 1.

3. The method of claim 2, wherein: when ring A is C_6-16When it is aromatic, the C_6-16The aromatic ring is a benzene ring or a naphthalene ring;

and/or, when ring a is a 5-16 membered heteroaryl ring, said 5-16 membered heteroaryl ring is a pyridine ring;

and/or when R³Is C_1-6When alkyl, said C_1-6Alkyl is methyl;

and/or when R³Is C_1-6At alkoxy, the C_1-6Alkoxy is methoxy;

and/or when R³Is C_1-6When halogenated alkyl, said C_1-6Haloalkyl is trifluoromethyl;

and/or when R¹Is C_1-6When alkyl, said C_1-6Alkyl is isopropyl;

and/or when R¹Is composed of

The above-mentioned

Is composed of

And/or when R¹Is C_6-16Aryl is said to C_6-16Aryl is phenyl or naphthyl;

and/or when R¹When 5-16 membered heteroaryl, said 5-16 membered heteroaryl is thienyl;

and/or when R^1-1Is C_1-6When alkyl, said C_1-6Alkyl is methyl;

and/or when R^1-1Is C_1-6At alkoxy radical, the C_1-6Alkoxy is methoxy;

and/or when R^1-1Is C_1-6When halogenated alkyl, said C_1-6Haloalkyl is trifluoromethyl;

and/or, when ring B is C_6-16When it is aromatic, the C_6-16The aromatic ring is a benzene ring, a naphthalene ring, an anthracene ring or a pyrene ring;

and/or, when ring B is a 5-16 membered heteroaromatic ring, said 5-16 membered heteroaromatic ring is a furan, thiophene, pyridine, pyrimidine, imidazole, benzopyridine or benzofuran ring;

and/or when R⁵Is C_1-6When alkyl, said C_1-6Alkyl is methyl;

and/or when R⁵Is C_1-6At alkoxy radical, the C_1-6Alkoxy is methoxy;

and/or when R⁵Is composed of

When is in use, the

Is trimethylsilyl;

and/or when R⁵Is composed of

When is in use, the

Is composed of

And/or when R⁵Is composed of

When is in use, the

Is composed of

And/or when R⁵Is composed of

When is in use, the

Is composed of

And/or when R⁵Is composed of

When is in use, the

Is composed of

And/or when R⁵Is C_1-6When halogenated alkyl, said C_1-6Haloalkyl is trifluoromethyl;

and/or when R⁴Is composed of

When is in use, the

Is composed of

And/or when R⁴Is composed of

When is in use, the

Is composed of

And/or when R¹⁰⁰Is C_1-4When alkyl, said C_1-4Alkyl is methyl;

and/or when R¹⁰⁰Is C_1-4At alkoxy, the C_1-4Alkoxy is methoxy;

and/or, when the base is an alkali metal carbonate, the alkali metal carbonate is one or more of sodium carbonate, potassium carbonate and cesium carbonate;

and/or, when the base is an alkali metal with C_1-4When the alkyl-COOH is a salt, the salt is a salt of an alkali metal and acetic acid, and/or a salt of an alkali metal and pivalic acid;

and/or, when the base is an alkali metal fluoride, the alkali metal fluoride is one or more of sodium fluoride, potassium fluoride and cesium fluoride;

and/or the molar ratio of the alkali to the compound shown in the formula I is 1.5-2: 1;

and/or, when the organic solvent is an ether solvent, the ether solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethylene glycol dimethyl ether, methyl tert-butyl ether, anisole and diethyl ether;

and/or when the organic solvent is an alkane solvent, the alkane solvent is n-hexane;

and/or, when the organic solvent is an alcohol solvent, the alcohol solvent is ethanol;

and/or, when the organic solvent is an aromatic solvent, the aromatic solvent is toluene;

and/or, when the organic solvent is an ester solvent, the ester solvent is ethyl acetate;

and/or, when the organic solvent is a halogenated hydrocarbon solvent, the halogenated hydrocarbon solvent is 1, 2-dichloroethane;

and/or, when the organic solvent is a nitrile solvent, the nitrile solvent is acetonitrile;

and/or, when the organic solvent is an amide solvent, the amide solvent is N, N-dimethylformamide;

and/or the reaction temperature is 80-110 ℃;

and/or the molar ratio of the compound shown as the formula II to the compound shown as the formula I is 3-5: 1;

and/or the palladium catalyst is one or more of tetrakis (triphenylphosphine) palladium, palladium acetate, palladium chloride, bis (triphenylphosphine) palladium dichloride, bis (cyanophenyl) palladium dichloride, diallyl palladium dichloride and bis (acetylacetonato) palladium;

and/or the molar ratio of the palladium catalyst to the compound shown in the formula I is 0.05-0.1: 1.

4. The method of claim 1, wherein: r¹Is C_1-6Alkyl, cyano,

Each z is independently 0,1, 2, 3 or 4;

and/or, R⁴Is composed of

And/or, the compound shown as the formula I is selected from any one of the following structures:

and/or the compound shown in the formula II is selected from any one of the following structures:

and/or the phosphine ligand is triphenylphosphine, tris (2-methoxyphenyl) phosphine, tris (3-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2,4, 6-trimethoxyphenyl) phosphine, tris (4-tolyl) phosphine, tris (3-fluorophenyl) phosphine, tris (4-fluorophenyl) phosphine, tris [4- (trifluoromethyl) phenyl ] phosphine, tris (2, 6-dimethoxyphenyl) phosphine, tris (2-furyl) phosphine, diphenyl-2-pyridylphosphine, benzyldiphenylphosphine, diphenylmethylphosphine, tricyclohexylphosphine tetrafluoroborate, bisdiphenylphosphinomethane, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphine) butane, 1, 5-bis (diphenylphosphine) pentane, tris (3-methoxyphenyl) phosphine, tris (4-fluorophenyl) phosphine, tris [ 4-fluorophenyl) phosphine ], tris [ 4-trifluoromethyl ] phosphine, tris (trifluoromethyl) phosphine, bis (2-methoxyphenyl) phosphine), tris (2-furyl) phosphine, 1, 5-bis (diphenylphosphine) pentane, bis (diphenylphosphine) butane, bis (diphenylphosphine), bis (2-methyl) pentane, bis (diphenylphosphine) ethane, 2-methyl) propane, bis (diphenylphosphine) ethane, bis (phenyl) propane, bis (diphenylphosphine) propane, bis (2-fluoro) propane, bis (phenyl) propane, bis (phenyl) propane, bis (2-phenyl) propane, bis (phenyl) propane, bis (2) propane, bis (phenyl) propane, bis (2) propane, bis (phenyl, One or more of 1, 6-bis (diphenylphosphino) hexane, 2-dicyclohexylphosphine-2 ',6' -dimethoxy-1, 1 '-biphenyl, 1' -bis (diphenylphosphino) ferrocene, 2-dicyclohexylphosphine-2 ',4',6 '-triisopropyl-1, 1' -biphenyl, 4, 5-bisdiphenylphosphino-9, 9-dimethylxanthene and bis (dicyclohexylphosphinophenyl) ether;

and/or the alkali is one or more of sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, sodium fluoride, potassium fluoride, cesium fluoride, sodium pivalate, potassium pivalate and cesium pivalate;

and/or the organic solvent is one or more of tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, ethylene glycol dimethyl ether, methyl tert-butyl ether, anisole, diethyl ether, N-hexane, ethanol, toluene, ethyl acetate, 1, 2-dichloroethane, acetonitrile and N, N-dimethylformamide.

5. The method of claim 1, wherein: r¹Is any one of the following structures:

and/or, X is Br;

and/or, R⁴Is composed of

And/or, the compound shown in the formula I is selected from any one of the following structures:

and/or the phosphine ligand is one or more of tri (2-methoxyphenyl) phosphine, tri (4-methoxyphenyl) phosphine, tricyclohexylphosphine tetrafluoroborate, 4, 5-bis (diphenylphosphino) -9, 9-dimethylxanthene and bis (dicyclohexylphosphinophenyl) ether;

and/or, the alkali is cesium and C_1-4Salts of alkyl-COOH;

and/or the organic solvent is tetrahydrofuran;

and/or the palladium catalyst is palladium acetate.

6. The method of claim 1, wherein: r¹Is any one of the following structures:

and/or, R⁴Is composed of

And/or the phosphine ligand is tri (2-methoxyphenyl) phosphine;

and/or the base is cesium pivalate.

7. The method of claim 1, wherein: the compound shown in the formula I is selected from any one of the following structures:

8. the method of claim 1, wherein: the compound shown in the formula III is of any one structure as follows: