BE1031909A1 - SYNTHESIS METHOD FOR THE ARYLBORATION OF OLEFINS BY PHOTOCATALYSIS - Google Patents

Abstract

The present invention discloses a synthetic method for the arylboration of olefins by photocatalysis. This method achieves an efficient and green synthesis of organoboron compounds under irradiation conditions using bispinacolatodiboranate (B2pin2), olefins, and aryl cyanide as starting materials. Under irradiation conditions, the oxidation of the photocatalyst results in the addition of the bispinacolatodiboranate/base complex to the olefins. At the same time, the resulting photocatalyst, in a reduced state, reduces the aryl cyanide to an anionic radical. Finally, the resulting boration intermediate radical of the olefins and the anionic radical of the aryl cyanide couple to form the 1,2-arylboration product of the olefins. The present invention utilizes inexpensive starting materials under photocatalytic conditions and applies them to the synthesis of organoboron compounds with potential biological activity. It has the potential to be developed for the industrial synthesis of functional organoboron compounds.

Description

DESCRIPTION '

SYNTHESIS METHOD FOR THE ARYLBORATION OF OLEFINS

BY PHOTOCATALYSIS

TECHNICAL AREA

The present invention relates to a synthesis method of photocatalytic organoboron compounds, in particular to a

Synthetic method for the arylboration of olefins by photocatalysis.

TECHNOLOGY IN THE BACKGROUND

Organoboron compounds are an important reactive group and are widely used in drug molecules, organic synthesis, and functional materials research. It is noteworthy that the Suzuki coupling reaction with organoboron compounds as

starting materials a variety of different

Carbon-carbon bonds can be formed. At the same time, the boron functional groups can be converted into various functional groups such as hydroxy and halogen groups. Therefore, the

Development of new synthesis methods for organoboron compounds has always been a research subject in organic synthesis.

The photocatalytic synthesis method has the advantages of mild

reaction conditions, high tolerance to functional groups and a wide range of substrates and is an important

Method of organic synthesis. The photocatalytic selective

Synthesis of organoboron compounds with high functionality from the cheap and readily available bispinacolatodiboranate, olefins and

Aryl cyanide is an atom- and stepwise economical, green and efficient synthesis strategy. However, the selective control of

Three-component reactions are usually difficult.

In the past, the catalytic coupling process of

Transition metals are used, but the control of the

Reaction selectivity was difficult and numerous by-products were usually formed, and there were disadvantages such as low

Compatibility of functional groups and harsh conditions, which often resulted in the scope of the reaction being limited.

The photocatalytic reaction is considered a green synthesis method in the

able to overcome the disadvantages caused by traditional transition metals. Therefore, the development of new synthesis methods for

Organoboron compounds under mild conditions and with simple

Handling has important practical significance. Based on the photocatalytic redox single electron transfer strategy, one can hope to realize multicomponent reactions under mild conditions and thus provide an effective route for the synthesis of

To provide organoboron compounds with high functionality.

In the past, the boronarylation of olefins was mainly achieved by the catalysis of transition metals such as nickel and palladium, but the synthetic strategy of arylboration of olefins on the

The basis of photocatalysis has not yet been reported in research. Considering that in the past, mainly transition metal catalysis was used for the synthesis of

Although the efficiency was high, it does not meet the requirements for the development of the modern green chemical industry and is difficult to apply on a large scale in industry. Through the photocatalytic synthesis of structurally diverse organoboron compounds from

A major breakthrough should be achieved by using bispinacolato diboranate, olefins, and aryl cyanide as three-component compounds. Furthermore, it is therefore very necessary to provide a new method for the preparation of photocatalytic organoboron.

CONTENT OF THE INVENTION

Aim of the invention: the present invention aims to provide a

To provide a synthetic method for the arylboration of olefins by photocatalysis, which serves to synthesize functional organoboron compounds and solves the problems encountered in the conventional synthesis routes of organoboron compounds, namely the dependence on

transition metals, the low compatibility, the narrow

Scope of application and simplicity of product structure.

Technical solution: the synthesis method of photocatalytic

Organoboron compounds according to the present invention comprise the following steps: the following steps: bispinacolatodiboranate,

Olefins, aryl cyanide, photocatalyst and base are converted into an organic

solvent is added and reacted under light exposure, and the reaction equation is as follows:

TN photocatalyst x

RA + Sapin ; Rte) LE à La

Bispinakalatodiboranate À, SP in the formula, R1 is selected from aryl or substituted aryl, wherein the substituent is one of the following: methyl, ethyl or halogen; Rz is one of the following: hydrogen, methyl or ethyl; Rs is selected from cyano; X is N or C; Bpin is pinacolboryl.

The present invention uses photocatalysis for the oxidation of

Bispinacolatodiboranate, base and olefins, whereby the alkyl

Radical of olefin boration is formed. Simultaneously, the reduced

state of the photocatalyst, the aryl cyanide to form the aryl anionic radical. The resulting alkyl radical of the

Olefinboration and the anionic radical of the aryl cyanide couple and undergo a decyanation process to form the desired

Organoboron compound.

Preferably, R is selected from aryl or substituted aryl, wherein the substituent is one of the following: methyl, ethyl or halogen; Ra is one of the following: hydrogen, methyl or ethyl; Rs is selected from cyano; X is N or C; Bpin is pinacolboryl.

Preferably, the photocatalyst is selected from tris(2-phenylpyridine)iridium.

Preferably the base is selected from potassium methoxide, sodium ethoxide,

Lithium tert-butoxide or potassium tert-butoxide is selected.

Preferably, the light source in the reaction is a blue light source with a wavelength of 450 to 455 nm and the power of the light source is 8 to 40 watts.

Preferably, the boron reagent is selected from bispinacolatodiboronate (abbreviated as Bzpin2).

Preferably, the olefins are obtained from styrene or a-methyl-substituted

Styrene is selected, and the aryl cyanide is selected from tetracyanopyridine or 1,4-phenylenedicyanine or at least one of the two.

Preferably, the organic solvent is selected from tetrahydrofuran or ethylene glycol dimethyl ether or at least one of the two.

Preferably, the molar ratio of aryl cyanide,

Bispinacolatodiboranate, olefins, photocatalyst and base 1 : 1 to 2 : 1 to 2 : 0.001 to 0.05 : 1 to 2.

Preferably, the temperature of the reaction is 20 to 30°C, the

Reaction time is 20 to 48 hours and the reaction is carried out under

Protection of an inert gas.

Preferably, the organoboron compounds have the structural formula of one of the following compounds:

CN CN CN CN

2 2 a 2 ‘Bu Me ® MeO CI 1 2 3 4

CN

CN CN ® © 2 wee:

Bpin Bpin < © 2 2 © 5 6 7

CN CN CN ï 1 Le © Bpin © Bpin N Bpin

DS D @ Oo 8 9 10

In the above technical solution,

Organoboron compounds by reaction with bispinacolatodiboranate 5 (Bzpinz), olefins, aryl cyanide, photocatalyst and base as

starting materials. In addition, this method is further used to

Postmodification of functional organoboron compound molecules with potential activity.

The present invention uses bispinacolatodiboranate (Bzpin2),

Olefins, aryl cyanide, photocatalyst and base as starting materials and the reaction produces organoboron compounds.

Production method uses photocatalysis for the oxidation of

Bispinacolatodiboranate, base and olefins, whereby the alkyl

Radical of olefin boration is formed. Simultaneously, the reduced

State of the photocatalyst, the aryl yanide to form the aryl anionic radical. The resulting alkyl radical of the

Olefinboration and the anionic radical of the aryl cyanide couple and undergo a decyanation process to form the desired

Organoboron compound. This reaction is associated with various

functional groups and can be used for post-modification and

transformation of functional organomolecules and has the value of developing new methods for the industrial synthesis of functional

organoboron compound molecules.

Advantages: Compared to existing technology, the present

The invention has the following significant advantages: it overcomes the disadvantages of traditional synthesis routes such as dependence on transition metals, low compatibility, narrow scope of application and

Uniformity of product structure. This method has mild

reaction conditions and is used to realize industrial

Mass production convenient.

DESCRIPTION OF THE ATTACHED DRAWING

Figure 1 shows the reaction route of the present invention.

DETAILED DESCRIPTION

In the following, the technical solution of the present invention is further explained with reference to the attached figure.

The embodiments of the present invention relate to the

Synthesis of the following compounds:

CN CN CN CN

2. 2. Le 2. ‘Bu Me ® MeO cl 1 2 3 4

CN

CN CN Ê

7 CG Xe

Bpin Bpin < © © © ° 6 7

CN CN CN

' &

D D @ ® 8 9 10

Example 1, the structural formula is: cn

A

{ + et Spin

Bee

The synthesis method is as follows: 5 1,4-phenylenedicyanoate (25.5 mg, 0.2 mmol, 1.0 equiv.), 4-tert-butylstyrene (64.1 mg, 0.4 mmol, 2.0 equiv.), bispinacolatodiboranate (Bzpina, 0.3 mmol, 76.2 mg, 1.5 equiv.), tris(2-phenylpyridine)iridium (2

mol%, 0.004 mmol), potassium phosphate (21 mg, 0.3 mmol, 1.5 equiv.), anhydrous tetrahydrofuran (1 mL). Under protection of

The mixture is sealed with nitrogen and stored at room temperature for 24

hours under blue light (wavelength 455 nm, power 40 W) for

reaction. Afterwards it is cooled, filtered, the

Solvent is recovered under reduced pressure and

column chromatography. This yields 47.5 mg of

Compound of Example 1 was obtained with a yield of 61%.

The structure was confirmed by NMR measurements; 'H NMR (400 MHz,

CDCIs): ò 7.59 - 7.50 (m, 2H), 7.40 - 7.36 (m, 2H), 7.30 - 7.26 (m, 2H), 7.16 - 7.12 (m, 2H), 4.28 (t, J = 8.5 Hz, 1H), 1.60 - 1.55 (d, J = 7.8 Hz, 2H), 1.27 (s, 9H), 1.05 (s, 6H), 1.03 (s, 6H) ppm. 13C{1H} NMR (100 MHz,

CDCls): 6 152.5, 149.4, 142.0, 132.2, 128.6, 127.3, 125.4, 119.2, 109.7, 83.4, 46.3, 34.4, 31.4, 24.7, 24.6, 19.0 ppm. ""B NMR (128 MHz, CDCks) 5 32.8 ppm.

Example 2, the structural formula is:

Me” =

The synthesis method is as follows: 1,4-phenylenedicyanoate (25.5 mg, 0.2 mmol, 1.0 equiv.), 4-methylstyrene (47.3 mg, 0.4 mmol, 2.0 equiv.), bispinacolatodiboranate (Bzpina, 0.3 mmol, 76.2 mg, 1.5 equiv.), tris(2-phenylpyridine)iridium (2

mol%, 0.004 mmol), potassium phosphate (21 mg, 0.3 mmol, 1.5 equiv.), anhydrous tetrahydrofuran (1 mL). Under protection of

The mixture is sealed with nitrogen and stored at room temperature for 24

hours under blue light (wavelength 455 nm, power 40 W) for

reaction. It is then cooled, filtered, and the

Solvent is recovered under reduced pressure and

column chromatography. This yields 41.7 mg of

Compound of Example 2 was obtained with a yield of 60%.

The structure was confirmed by NMR measurements; 'H NMR (400 MHz,

CDCIs): 5 7.56 - 7.49 (m, 2H), 7.37 - 7.34 (m, 2H), 7.12 - 7.05 (m, 4H), 4.28 (t, J = 8.4 Hz, 1H), 2.28 (s, 3H), 1.58 - 1.54 (m, 2H), 1.06 (s, 12H) ppm. 13C{1H} NMR (100 MHz, CDCls): 5 152.6, 142.1, 136.1, 132.2, 129.3, 128.5, 127.5, 119.2, 109.7, 83.4, 46.3, 24.7, 21.0, 19.0 ppm. 11B NMR (128

MHz, CDCls) at 30.6 ppm.

Example 3, the structural formula is:

U

"te £ - Spin mo

The synthesis method is as follows: 1,4-phenylenedicyanoate (25.5 mg, 0.2 mmol, 1.0 equiv.), 4-methoxystyrene (53.7 mg, 0.4 mmol, 2.0 equiv.), bispinacolatodiboranate (Bzpina, 0.3 mmol, 76.2 mg, 1.5 equiv.), tris(2-phenylpyridine)iridium (2

mol%, 0.004 mmol), potassium phosphate (21 mg, 0.3 mmol, 1.5 equiv.), anhydrous tetrahydrofuran (1 mL). Under protection of

The mixture is sealed with nitrogen and stored at room temperature for 24

hours under blue light (wavelength 455 nm, power 40 W) for

reaction. It is then cooled, filtered, and the

Solvent is recovered under reduced pressure and

Column chromatography was used to separate the product. This yielded 40 mg of the compound of Example 3, with a yield of 55%.

The structure was confirmed by NMR measurements; 'H NMR (400 MHz,

CDCIs): ò 7.57 — 7.50 (m, 2H), 7.36 — 7.33 (m, 2H), 7.15 — 7.11 (m, 2H), 6.83 — 6.79 (m, 2H), 4.28 (t, J = 8.4 Hz, 1H), 3.76 (s, 3H), 1.58 — 1.51 (m, 2H), 1.07 (s, 12H) ppm. 13C{1H} NMR (100 MHz, CDCls): 5 158.2, 152.8, 137.2, 132.2, 128.6, 128.4, 119.2, 113.9, 109.7, 83.4, 55.3, 45.8, 24.6, 19.1 ppm. 11B NMR (128 MHz, CDCl3) 5 34.5 ppm.

Example 4, the structural formula is:

10 2 à a A Brin

The synthesis method is as follows: 1,4-phenylenedicyanoate (25.5 mg, 0.2 mmol, 1.0 equiv.), 4-chlorostyrene (55.4 mg, 0.4 mmol, 2.0 equiv.), bispinacolatodiboranate (Bzpina, 0.3 mmol, 76.2 mg, 1.5 equiv.), tris(2-phenylpyridine)iridium (2

mol%, 0.004 mmol), potassium phosphate (21 mg, 0.3 mmol, 1.5 equiv.), anhydrous tetrahydrofuran (1 mL). Under protection of

The mixture is sealed with nitrogen and stored at room temperature for 24

hours under blue light (wavelength 455 nm, power 40 W) for

reaction. It is then cooled, filtered, and the

Solvent is recovered under reduced pressure and

column chromatography. This yields 46.3 mg of

Compound of Example 4 was obtained with a yield of 63%.

The structure was confirmed by NMR measurements; "H NMR (400 MHz,

CDCIs): ò 7.60 - 7.51 (m, 2H), 7.34 - 7.31 (m, 2H), 7.26 - 7.21 (m, 2H), 7.16 - 7.13 (m, 2H), 4.29 (t, J = 8.3 Hz, 1H), 1.56 - 1.52 (m, 2H), 1.07 (s, 12H) ppm. 13C{1H} NMR (100 MHz, CDCks): 5 151.7, 143.5, 132.3, 129.1, 129.0, 128.7, 128.5, 119.0, 110.1, 83.5, 46.0, 24.7, 18.9 ppm. 11B NMR (128 MHz, CDCIs) 5 33.1 ppm.

Example 5, the structural formula is: et DD

The synthesis method is as follows: 1,4-phenylenedicyanin (25.5 mg, 0.2 mmol, 1.0 equiv.), a-methylstyrene (47.3 mg, 0.4 mmol, 2.0 equiv.), bispinacolatodiboranate

(B2pin2, 0.3 mmol, 76.2 mg, 1.5 equiv.), Tris(2-phenylpyridine)iridium (2

mol%, 0.004 mmol), potassium phosphate (21 mg, 0.3 mmol, 1.5 agequiv.), anhydrous tetrahydrofuran (1 mL). Under protection of

The mixture is sealed with nitrogen and stored at room temperature for 24

hours under blue light (wavelength 455 nm, power 40 W) for

reaction. It is then cooled, filtered, and the

Solvent is recovered under reduced pressure and

column chromatography. This yields 54.1 mg of

Compound of Example 5 was obtained with a yield of 78%.

The structure was confirmed by NMR measurements; 'H NMR (400 MHz,

CDCIs): ò 7.59 - 7.51 (m, 2H), 7.38 - 7.35 (m, 2H), 7.30 - 7.25 (m, 2H), 7.23 - 7.17 (m, 3H), 1.81 (s, 3H), 1.75 - 1.70 (m, 2H), 1.03 (s, 12H) ppm. 13C{1H} NMR (100 MHz, CDCIs): 5 157.0, 149.8, 131.7, 128.1, 128.0, 127.0, 126.1, 119.2, 109.3, 83.1, 45.0, 29.7, 26.0, 24.6 ppm. 11B NMR (128 MHz,

CDCls) ò 32.4 ppm.

Example 6, the structural formula is:

CN

A Sp

The synthesis method is as follows: 1,4-phenylenedicyan (25.5 mg, 0.2 mmol, 1.0 equiv.), 1-methyl-4-(1-methylvinyl)benzene (52.8 mg, 0.4 mmol, 2.0 equiv.),

Bispinakolatodiboranate (B2pinz, 0.3 mmol, 76.2 mg, 1.5 ag.),

Tris(2-phenylpyridine)iridium (2 mol%, 0.004 mmol), potassium phosphate (21 mg, 0.3 mmol, 1.5 equiv.), anhydrous tetrahydrofuran (1 mL).

Under nitrogen protection, the mixture is sealed and at

The reaction mixture was allowed to proceed at room temperature for 24 hours under blue light (wavelength 455 nm, power 40 W). It was then cooled, filtered, the solvent recovered under reduced pressure, and separated by column chromatography. This yielded 52.0 mg of the compound of Example 6, with a yield of 72%.

The structure was confirmed by NMR measurements; 'H NMR (400 MHz,

CDCIs): ò 7.56 - 7.48 (m, 2H), 7.36 - 7.33 (m, 2H), 7.07 (s, 4H), 2.30 (s, 3H), 1.78 (s, 3H), 1.69 (s, 1H), 1.01 (s, 12H) ppm. !SC{1H} NMR (100 MHz,

CDCls): ò 157.1, 147.0, 135.5, 131.7, 128.8, 128.0, 126.8, 119.2, 109.2, 83.0, 44.6, 29.7, 26.1, 24.6, 20.9 ppm. ""B NMR (128 MHz, CDCIs) 5 32.8 ppm.

Example 7, the structural formula is: ® oh

DA 1,4-phenylenedicyan (25.5 mg, 0.2 mmol, 1.0 equiv.), 5-benzod[1,3]dioxolylvinyl (64.8 mg, 0.4 mmol, 20 equiv.),

Bispinakolatodiboranate (B2pinz2, 0.3 mmol, 76.2 mg, 1.5 ag.),

Tris(2-phenylpyridine)iridium (2 mol%, 0.004 mmol), potassium phosphate (21 mg, 0.3 mmol, 1.5 equiv.), anhydrous tetrahydrofuran (1 mL).

Under nitrogen protection, the mixture is sealed and at

The reaction mixture was allowed to proceed at room temperature for 24 hours under blue light (wavelength 455 nm, power 40 W). It was then cooled, filtered, the solvent was recovered under reduced pressure, and separated by column chromatography. This yielded 59.4 mg of the compound of Example 7, with a yield of 76%.

The structure was confirmed by NMR measurements; 'H NMR (400 MHz,

CDCls): 5 7.57 - 7.49 (m, 2H), 7.36 - 7.33 (m, 2H), 6.72 - 6.66 (m, 2H), 6.63 - 6.61 (m, 1H), 5.90 (s, 2H), 1.75 (s, 3H), 1.65 (s, 2H), 1.03 (s, 12H) ppm. 13C{1H} NMR (100 MHz, CDCls): 5 157.0, 147.5, 145.7, 144.1, 131.8, 127.9, 119.9, 119.2, 109.4, 108.1, 107.6, 101.0, 83.1, 44.8, 29.9, 26.5, 24.7 ppm. 11B NMR (128 MHz, CDCIs) 5 33.4 ppm.

Example 8, the structural formula is:

CN

OO ee À DD

JJ Ds

The synthesis method is as follows: 1,4-phenylenedicyan (25.5 mg, 0.2 mmol, 1.0 equiv.), a-cyclopropylstyrene (57.6 mg, 0.4 mmol, 2.0 equiv.),

Bispinakolatodiboranate (B2pinz, 0.3 mmol, 76.2 mg, 1.5 ag.),

Tris(2-phenylpyridine)iridium (2 mol%, 0.004 mmol), potassium phosphate (21 mg, 0.3 mmol, 1.5 equiv.), anhydrous tetrahydrofuran (1 mL).

Under nitrogen protection, the mixture is sealed and at

The reaction mixture was allowed to proceed at room temperature for 24 hours under blue light (wavelength 455 nm, power 40 W). It was then cooled, filtered, the solvent was recovered under reduced pressure, and separated by column chromatography. This yielded 43.3 mg of the compound of Example 8, with a yield of 58%.

The structure was confirmed by NMR measurements; 'H NMR (400 MHz,

CDCls): ò 7.73 — 7.64 (m, 2H), 7.58 — 7.55 (m, 2H), 7.40 — 7.35 (m, 2H), 7.33 — 7.26 (m, 3H), 2.08 — 1.98 (m, 3H), 1.11 (s, 12H), 0.69 — 0.61 (m, 2H), 0.09 —-0.05 (m, 2H) ppm. 'SC{1H} NMR (100 MHz, CDCls): 5 154.6, 146.4, 131.2, 129.7, 128.9, 127.5, 126.2, 119.3, 109.5, 83.0, 48.8, 24.6, 24.5, 19.8, 1.9, 1.5 ppm. 11B NMR (128 MHz, CDCIs) at 33.0 ppm.

Example 9, the structural formula is:

The synthesis method is as follows: 1,4-phenylenedicyanoate (25.5 mg, 0.2 mmol, 1.0 equiv.), a-cyclobutylstyrene (63.3 mg, 0.4 mmol, 2.0 equiv.), bispinacolatodiboranate (Bzpina, 0.3 mmol, 76.2 mg, 1.5 equiv.), tris(2-phenylpyridine)iridium (2

mol%, 0.004 mmol), potassium phosphate (21 mg, 0.3 mmol, 1.5 equiv.), anhydrous tetrahydrofuran (1 mL). Under protection of

The mixture is sealed with nitrogen and stored at room temperature for 24

hours under blue light (wavelength 455 nm, power 40 W) for

reaction. It is then cooled, filtered, and the

Solvent is recovered under reduced pressure and

column chromatography. This yields 56.5 mg of

Compound of Example 9 was obtained with a yield of 73%.

The structure was confirmed by NMR measurements; "H NMR (400 MHz,

CDCls): ò 7.53 - 7.46 (m, 2H), 7.25 - 7.19 (m, 4H), 7.17 - 7.13 (m, 1H), 7.07 - 7.04 (m, 2H), 3.55 - 3.48 (m, 1H), 1.96 - 1.89 (m, 2H), 1.77 - 1.61 (m, 2H), 1.59 - 1.50 (m, 3H), 1.34 - 1.25 (m, 1H), 0.94 (s, 12H) ppm. 13C{1H} NMR (100 MHz, CDCIs): 5 154.7, 147.2, 131.1, 129.8, 128.9, 127.6, 126.0, 119.3, 109.3, 82.9, 51.0, 42.3, 24.8, 24.6, 22.0, 17.4 ppm. ""B NMR (128 MHz, CDCIs) 5 32.2 ppm.

Example 10, the structural formula is: era

The synthesis method is as follows: 1,4-phenylenedicyan (25.5 mg, 0.2 mmol, 1.0 equiv.), 9-ethyl-2-(propyl-1-en-2-yl)-9H-carbazole (63.3 mg, 0.4 mmol, 2.0 equiv.),

Bispinakolatodiboranate (Bzpina, 0.3 mmol, 76.2 mg, 1.5 ag.),

Tris(2-phenylpyridine)iridium (2 mol%, 0.004 mmol), potassium phosphate (21 mg, 0.3 mmol, 1.5 equiv.), anhydrous tetrahydrofuran (1 mL).

Under nitrogen protection, the mixture is sealed and at

The reaction mixture was allowed to proceed at room temperature for 24 hours under blue light (wavelength 455 nm, power 40 W). It was then cooled, filtered, the solvent recovered under reduced pressure, and separated by column chromatography. This yielded 63.1 mg of the compound of Example 8, with a yield of 68%.

The structure was confirmed by NMR measurements; 'H NMR (400 MHz,

CDCl): 5 8.08 - 8.05 (m, 2H), 7.78 (s, 1H), 7.55 - 7.52 (m, 2H), 7.43 - 7.39 (m, 4H), 7.23 - 7.17 (m, 2H), 4.34 (d, J = 7.2 Hz, 2H), 1.93 (s, 3H), 1.85 (d, J = 9.6 Hz, 2H), 1.42 (d, J = 7.2 Hz, 3H), 0.99 (s, 12H) ppm. 13C{1H} NMR (100 MHz, CDCIs): 5 158.0, 140.5, 138.3, 132.8, 131.7, 128.1, 125.8, 125.6, 123.1, 122.4, 120.3, 119.4, 118.8, 118.1, 109.1, 108.6, 108.3, 83.0, 45.0, 37.6, 30.3, 27.0, 24.7, 13.9 ppm. ""B NMR (128 MHz, CDCks) 5 34.0 ppm.

Example 11

Based on the working example 8, the photocatalyst is modified. The synthesis method is as follows: 1,4-phenylenedicyanoin (25.5 mg, 0.2 mmol, 1.0 equiv.), a-cyclobutylstyrene (63.3 mg, 0.4 mmol, 2.0 equiv.), bispinacolatodiboranate (Bzpina, 0.4 mmol, 101.57 mg, 2 equiv.), tris(2-phenylpyridine)iridium (2

mol%, 0.004 mmol), potassium phosphate (21 mg, 0.3 mmol, 1.5 equiv.), anhydrous tetrahydrofuran (1 mL). Under protection of

The mixture is sealed with nitrogen and stored at room temperature for 24

hours under blue light (wavelength 455 nm, power 40 W) for

reaction. It is then cooled, filtered, and the

Solvent is recovered under reduced pressure and

column chromatography. This yields 52.6 mg of

Compound of Example 8 was obtained with a yield of 68%.

Claims (10)

PATENT CLAIMS 1. A synthetic method of arylboration of olefins by photocatalysis, which is characterized in that it comprises the following steps: bispinacolatodiboranate = (Bazpin2), olefins, aryl cyanide, photocatalyst and base are introduced into an organic solvent and reacted under irradiation, and the reaction equation is as follows: Is photocatalyst x = N Rf) base nt) Ri Sen + Sag + SET se ee bispinacolatodiboranate Rs 8 A, Sp X= NC in the formula, Rı is selected from aryl or substituted aryl, wherein the substituent is one of the following: methyl, ethyl or halogen; Re is one of the following: hydrogen, methyl or ethyl; Rs is selected from cyano; X is N or C; Bpin stands for pinacolboranyl. 2. The synthesis method of arylboration of olefins by photocatalysis according to claim 1, characterized in that the aryl cyanide is selected from tetracyanopyridine or 1,4-phenylenedicyanide. 3. The synthesis method of arylboration of olefins by photocatalysis according to claim 1, characterized in that the photocatalyst is selected from tris(2-phenylpyridine)iridium, and the boron reagent is selected from bispinacolatodiboranate (abbreviated as Bzpin2). 4 The synthesis method of arylboration of olefins by photocatalysis according to claim 1, characterized in that the base is selected from potassium methoxide, sodium ethoxide, lithium tert-butoxide or potassium tert-butoxide. 5. The synthesis method of arylboration of olefins by photocatalysis according to claim 1, characterized in that the light source in the reaction is a blue light source having a wavelength of 450 to 455 nm and the power of the light source is 8 to 40 watts. 6. The synthesis method of arylboration of olefins by photocatalysis according to claim 1, characterized in that the olefins are selected from styrene or a-methyl-substituted styrene, and the aryl cyanide is selected from tetracyanopyridine or 1,4-phenylenedicyanine or at least one of the two. 7. The synthesis method of arylboration of olefins by photocatalysis according to claim 1, characterized in that the organic solvent is selected from tetrahydrofuran or ethylene glycol dimethyl ether or at least one of the two. 8. The synthesis method of arylboration of olefins by photocatalysis according to claim 1, characterized in that the molar ratio of = aryl cyanide, bispinacolato diboranate, olefins, photocatalyst and base is 1: 1 to 2: 1 to 2: 0.001 to 0.05: 1 to 2. 9. The synthesis method of arylboration of olefins by photocatalysis according to claim 1, characterized in that the reaction temperature is 20 to 30°C, the reaction time is 20 to 48 hours and the reaction is carried out under the protection of an inert gas. 10. The synthesis method for the arylboration of olefins by photocatalysis according to claim 1, characterized in that the organoboron compounds have the structural formula of one of the following compounds: