Method for light / cobalt redox catalytic coupling reaction of aryl halide and Hanss ester

Abstract

The invention discloses a method for catalyzing a coupling reaction of aryl halide and Hanus ester by light / cobalt redox, which comprises the following steps: adding a photocatalyst and cobalt salt into a solvent containing organic amine and zinc salt, and catalyzing the coupling reaction of aryl halide and Hanus ester to synthesize diphenylmethane compounds and derivatives thereof under the irradiation of visible light. According to the method disclosed by the invention, the Hanus ester is used as a mild free radical precursor to replace a traditional metal reagent to carry out coupling reaction with the aryl halide, so that the substrate compatibility and the reaction operability are improved, and the product yield can be up to 93%.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic synthesis, and particularly relates to a method for coupling reaction of aryl halide and Hans ester through light / cobalt redox catalysis. BACKGROUND

[0002] Coupling reaction, also known as coupling reaction, coupling reaction and coupling reaction, is a process of obtaining an organic molecule by the chemical reaction of two organic chemical units. The narrow sense of coupling reaction refers to the carbon-carbon bond formation reaction involving an organic metal catalyst. Among them, the transition metal-catalyzed carbon-carbon coupling reaction (such as Suzuki, Negishi, Kumada, etc.) is an important method for building complex molecules in organic synthesis. Among the commonly used transition metal catalysts, palladium (Pd) and nickel (Ni) catalysts are widely used due to their high efficiency, but the traditional Pd / Ni catalysts are high in cost, high in toxicity, and dependent on organic metal reagents (such as Grignard reagent), which limits the functional group compatibility. Cobalt has been widely concerned due to its advantages of abundant reserves, low price and low toxicity. Studies have shown that cobalt catalysts exhibit different reaction characteristics in carbon-carbon coupling reactions, especially in the coupling reaction of alkyl halides, which can effectively inhibit the beta-H elimination and other side reactions. However, the existing cobalt catalytic system still has obvious deficiencies: most of the reactions still need to use Grignard reagent and other strong nucleophilic reagents, which limits the compatibility of functional groups. SUMMARY

[0003] In view of the deficiencies of the prior art, the purpose of the present application is to provide a method for coupling reaction of aryl halide and Hans ester through light / cobalt redox catalysis, which synthesizes a series of diphenylmethane compounds and their derivatives with medical value and industrial perfume application value, without using organic metal reagents, and compatible with a variety of functional groups, and has high yield.

[0004] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0005] The method for coupling reaction of aryl halide and Hans ester through light / cobalt redox catalysis provided by the present application adds a photocatalyst and a cobalt salt in a solvent containing an organic amine and a zinc salt, and under visible light irradiation, catalyzes the coupling reaction of aryl halide and Hans ester to synthesize diphenylmethane compounds and their derivatives;

[0006] The aryl halide is a compound shown in formula 1,

[0007]

[0008] Among them, Ar is a benzene ring, naphthalene ring or aromatic heterocycle substituted with one of ketone carbonyl, aldehyde group, cyano, phenyl, trifluoromethyl, fluorine, chlorine and hydrogen, and X is Br or I;

[0009] The Hans ester is a compound shown in formula 2,

[0010]

[0011] R is one of benzyl, halogenated benzyl, alkyl or alkoxy substituted benzyl, carbazolyl and indolyl.

[0012] Further, the cobalt salt is at least one of cobalt fluoride, cobalt chloride, cobalt bromide, cobalt iodide, cobalt acetate, cobalt acetylacetonate, cobalt iso-octoate and cobalt hypochlorite, and the amount is 0.0002-0.30 equivalent.

[0013] Further, the photocatalyst is a CzIPN catalyst or a CzIPN derivative catalyst, and the amount is 0.0001-0.2 equivalent.

[0014] Further, the organic amine is at least one of methylamine, diethylamine, triethylamine, N,N-diisopropylethylamine (DIPEA), tetramethyl ethylenediamine (TMEDA) and triethylenediamine (DABCO), and the amount is 0.5-8 equivalent.

[0015] Further, the zinc salt is at least one of zinc sulfate, zinc carbonate, zinc oxide, zinc sulfide, zinc bromide, zinc acetate, zinc stearate and zinc lactate.

[0016] Further, the solvent is at least one of nitrile solvent, halogenated alkane solvent, amide solvent, sulfoxide solvent and water.

[0017] Further, the solvent is at least one of acetonitrile, water, dichloromethane, trichloromethane, 1,2-dichloroethane, N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide.

[0018] Further, the wavelength of the visible light is 360-500 nm.

[0019] Further, the reaction temperature of the coupling reaction is 15-50℃, and the reaction time is 12-36 hours.

[0020] Compared with the prior art, the present application has the following beneficial effects:

[0021] In the present application, Hans ester is used as a mild free radical precursor to replace traditional metal reagents and aryl halides for coupling reaction, which improves the substrate compatibility and the operability of the reaction, and the product yield can be as high as 93%. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 It is a reaction mechanism diagram of the light / cobalt redox catalytic aryl halide and Hans ester coupling reaction of the present application. DETAILED DESCRIPTION

[0023] The application will be further described in conjunction with specific examples to make those skilled in the art have a clearer understanding of the application. The examples are only used to explain the application, and are not used to limit the scope of the application. In the examples of the application, all raw material components are commercially available products well known to those skilled in the art, unless otherwise specified. If not specifically indicated, the technical means used are conventional means well known to those skilled in the art.

[0024] Example 1

[0025]

[0026] The reaction mechanism is shown as follows: Figure 1 The preparation method of compound 3aa is as follows:

[0027] In an argon-filled glove box, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene 1a (0.20 mmol), Hanstzch ester 2a (0.30 mmol), zinc bromide (0.40 mmol) and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5W blue LED. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3aa. Target product 43.3 mg, yield 90%.

[0028] 1 H NMR (400 MHz, CDCl3) δ (ppm) 7.95 (d, J = 8.0 Hz, 2H), 7.31-7.21 (m, 4H), 7.21-7.18 (m, 3H), 4.20 (q, J = 7.2 Hz, 1H), 3.89 (s, 3H), 1.65 (d, J = 7.2 Hz, 3H). 13 C NMR (100 MHz, CDCl3) δ (ppm) 167.1, 151.7, 145.5, 129.8, 128.5, 128.0, 127.7, 127.6, 126.3, 52.0, 44.8, 21.6. HRMS (ESI): m / z [M+H] + calcd. for C 16 H 17 O2 + : 241.1223, found 241.1230.

[0029] Example 2

[0030]

[0031] The preparation method of compound 3ab is as follows:

[0032] In an argon-filled glove box, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene la (0.20 mmol), Hanstzch ester 2b (0.30 mmol), zinc bromide (0.40 mmol) and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5W blue LED. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3ab. Target product 41.8 mg, 92% yield.

[0033] 1 H NMR (400 MHz, CDC13) d (ppm) 7.95 (d, J = 8.0 Hz, 2H), 7.32-7.12 (m, 7H), 4.03 (s, 2H), 3.89 (s, 3H). 13 C NMR (100 MHz, CDC13) d (ppm) 167.1, 146.5, 140.1, 129.8, 128.9, 128.6, 128.0, 126.4, 52.0, 41.9. HRMS (ESI): m / z [M+H] + calcd. for C 15 H 15 O2 + : 227.1067, found 227.1071.

[0034] Example 3

[0035]

[0036] The preparation method of compound 3ac is as follows:

[0037] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene la (0.20 mmol), Hanstzch ester 2c (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5 W blue LED. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3ac. Target product 43.0 mg, 88% yield.

[0038] 1 H NMR (400 MHz, CDC13) δ (ppm) 7.96 (d, J = 8.0 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 7.14-7.09 (m, 2H), 7.00-6.94 (m, 2H), 3.99 (s, 2H), 3.89 (s, 3H). 13 C NMR (100 MHz, CDC13) δ (ppm) 167.0, 162.8, 160.4, 146.3, 135.8 (d, J = 3.0 Hz), 130.4 (d, J = 8.0 Hz), 129.9, 128.9, 128.2, 115.4 (d, J = 21.3 Hz), 52.0, 41.0. 19 F NMR (376 MHz, CDC13) δ -116.77. HRMS (ESI): m / z [M + H] + calcd. for C 15 H 14 FO2 + : 245.0972, found 245.0977.

[0039] Example 4

[0040]

[0041] The compound 3ad was prepared as follows:

[0042] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene la (0.20 mmol), Hanstzch ester 2d (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature under a 5W blue LED for 24 h. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3ad. Target product 45.3 mg, 87% yield.

[0043] 1 H NMR (400 MHz, CDC13) δ (ppm) 7.96 (d, J = 8.0 Hz, 2H), 7.27-7.21 (m, 4H), 7.09 (d, J = 8.0 Hz, 2H), 3.98 (s, 2H), 3.89 (s, 3H). 13 C NMR (100 MHz, CDC13) δ (ppm) 167.0, 145.9, 138.6, 132.3, 130.3, 129.9, 128.9, 128.7, 128.3, 52.1, 41.2. HRMS (ESI): m / z [M + Na] + calcd. for C 15 H 13 ClNaO2 + : 283.0496, found 283.0493.

[0044] Example 5

[0045]

[0046] The compound 3ae was prepared as follows:

[0047] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene la (0.20 mmol), Hanstzch ester 2d (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature under a 5W blue LED for 24 h. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3ad. Target product 45.3 mg, 87% yield.

[0048] 1H NMR (400 MHz, CDC13) δ (ppm) 7.94 (d, J = 8.0 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 7.08 (d, J = 8.0 Hz, 2H), 6.83 (d, J = 8.0 Hz, 2H), 3.96 (s, 2H), 3.88 (s, 3H), 3.77 (s, 3H). 13 C NMR (100 MHz, CDC13) δ (ppm) 147.0, 132.2, 129.9, 129.7, 128.8, 127.9, 114.0, 55.2, 51.9, 41.0. HRMS (ESI): m / z [M + H] + calcd. for C 16 H 17 O3 + : 257.1172, found 257.1172.

[0049] Example 6

[0050]

[0051] Compound 3af was prepared as follows:

[0052] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene la (0.20 mmol), Hanstzch ester 2f (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5 W blue LED. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3af. Target product 42.2 mg, 88% yield.

[0053] 1 H NMR (400 MHz, CDC13) δ (ppm) 7.94 (d, J = 8.0 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 7.08 (d, J = 8.0 Hz, 2H), 6.83 (d, J = 8.0 Hz, 2H), 3.96 (s, 2H), 3.88 (s, 3H), 3.77 (s, 3H). 13C NMR (100 MHz, CDC13) δ 167.1, 146.7, 140.1, 138.3, 129.8, 129.0, 128.5, 128.1, 127.1, 126.0, 52.0, 41.9, 21.4. HRMS (ESI): m / z [M+H] + calcd. for C 16 H 17 O2 + : 241.1223, found 241.1224.

[0054] Example 7

[0055]

[0056] Compound 3ag was prepared as follows:

[0057] In an argon-filled glove box, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene la (0.20 mmol), Hanstzch ester 2g (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5 W blue LED. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3ag. 42.8 mg, 89% yield.

[0058] 1 H NMR (400 MHz, CDC13) δ (ppm) 7.94 (d, J = 8.0 Hz, 2H), 7.19-7.15 (m, 5H), 7.11-7.08 (m, 1H), 4.03 (s, 2H), 3.89 (s, 3H), 2.21 (s, 3H). 13 C NMR (100 MHz, CDC13) δ (ppm) 167.1, 146.0, 138.0, 136.7, 130.5, 130.0, 129.8, 128.7, 128.0, 126.8, 126.1, 52.0, 39.6, 19.7. HRMS (ESI): m / z [M+H] + calcd. for C 16 H 17 O2 + : 241.1223, found 241.1224.

[0059] Example 8

[0060]

[0061] The preparation method of compound 3ah is as follows:

[0062] In an argon-filled glove box, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 minutes, 4CzIPN (0.004 mmol, 3.2 mg), bromoaryl 1a (0.20 mmol), Hanstzsch ester 2h (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature under a 5 W blue LED for 24 hours. The mixture was then concentrated in vacuo, and the residue was purified by silica gel flash column chromatography to obtain the desired product 3ah. 46.5 mg of the target product was obtained in an 86% yield.

[0063] 1 H NMR (400MHz, CDCl3) δ (ppm) 7.94 (d, J = 8.0Hz, 2H), 7.19-7.15 (m, 5H), 7.11-7.08 (m, 1H), 4.03 (s, 2H), 3.89 (s, 3H), 2.21 (s, 3H). 13 C NMR (100MHz, CDCl3) δ (ppm) 167.1, 146.0, 138.0, 136.7, 130.5, 130.0, 129.8, 128.7, 128.0, 126.8, 126.1, 52.0, 39.6, 19.7. HRMS (ESI): m / z [M+H] + calcd.for C 16 H 17 O2 + :241.1223,found 241.1224.

[0064] Example 9

[0065]

[0066] The preparation method of compound 3ai is as follows:

[0067] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene la (0.20 mmol), Hanstzch ester 2i (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature under a 5W blue LED for 24 h. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3ai. Target product 42.0 mg, 65% yield.

[0068] 1 H NMR (400 MHz, CDC13) d (ppm) 7.94 (d, J = 8.0 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 4.56 (s, 2H), 3.84 (s, 3H), 3.75 (t, J = 5.2 Hz, 2H), 3.51 (t, J = 5.2 Hz, 2H), 0.83 (s, 9H). 13 C NMR (100 MHz, CDC13) d (ppm) 167.0, 143.9, 129.6, 129.2, 127.0, 72.6, 72.1, 62.8, 52.1, 25.9, 18.4, -5.2. HRMS (ESI): m / z [M + H] + calcd. for C 17 H 29 O4Si + : 325.1830, found 325.1830.

[0069] Example 10

[0070]

[0071] The compound 3aj was prepared as follows:

[0072] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene la (0.20 mmol), Hanstzch ester 2i (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature under a 5W blue LED for 24 h. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3ai. Target product 42.0 mg, 65% yield.

[0070]

[0071] The compound 3aj was prepared as follows:

[0072] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene la (0.20 mmol), Hanstzch ester 2i (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature under a 5W blue LED for 24 h. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3ai. Target product 42.0 mg, 65% yield.

[0073] 1 H NMR (400 MHz, CDC13) δ (ppm) 8.02 (d, J = 8.0 Hz, 2H), 7.43 (d, J = 8.0 Hz, 2H), 7.37-7.36 (m, 4H), 7.34-7.29 (m, 1H), 4.60 (s, 2H), 4.58 (s, 2H), 3.91 (s, 3H). 13 C NMR (100 MHz, CDC13) δ (ppm) 167.0, 143.6, 137.9, 129.7, 129.4, 128.5, 127.8, 127.3, 72.5, 71.5, 52.1. HRMS (ESI): m / z [M+H] + calcd. for C 16 H 17 O3 + :257.1172, found 257.1175.

[0074] Example 11

[0075]

[0076] The compound 3ak was prepared as follows:

[0077] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene la (0.20 mmol), Hanstzch ester 2k (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5 W blue LED. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3ak. Target product 40.0 mg, 64% yield.

[0078] 1 H NMR (400 MHz, CDC13) δ (ppm) 8.02 (d, J = 8.0 Hz, 2H), 7.43 (d, J = 8.0 Hz, 2H), 7.37-7.36 (m, 4H), 7.34-7.29 (m, 1H), 4.60 (s, 2H), 4.58 (s, 2H), 3.91 (s, 3H). 13CNMR (100 MHz, CDC13) δ (ppm) 166.7, 142.4, 140.5, 130.1, 129.5, 126.4, 126.0, 123.1, 120.5, 119.5, 108.7, 52.1, 46.4. HRMS (ESI): m / z [M+H] + calcd. for C 21 H 18 NO2 + : 316.1332, found: 3165.1330.

[0079] Example 12

[0080]

[0081] Compound 3al was prepared as follows:

[0082] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene la (0.20 mmol), Hanstzch ester 2l (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5 W blue LED. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3al. Target product 52.1 mg, 82% yield.

[0083] 1 H NMR (400 MHz, CDC13) δ (ppm) 7.97 (d, J = 8.0 Hz, 2H), 7.41 (d, J = 8.1 Hz, 2H), 7.23 (t, J = 8.0 Hz, 4H), 7.04 (d, J = 8.0 Hz, 4H), 6.94 (t, J = 8.0 Hz, 2H), 5.03 (s, 2H), 3.88 (s, 3H). 13 CNMR (100 MHz, CDC13) δ (ppm) 167.0, 147.8, 144.8, 130.0, 129.4, 128.9, 126.6, 121.7, 120.7, 56.3, 52.1. HRMS (ESI): m / z [M+H] + calcd. for C 21 H 20 NO2 + : 318.1489, found 318.1487.

[0084] Example 13

[0085]

[0086] Compound 3am was prepared as follows:

[0087] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene la (0.20 mmol), Hanstzch ester 2m (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5 W blue LED. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3am. 36.0 mg, 55% yield.

[0088] 1 H NMR (400 MHz, CDC13) d (ppm) 8.12 (d, J = 8.0 Hz, 2H), 7.97 (d, J = 8.0 Hz, 2H), 7.36 - 7.32 (m, 4H), 7.26 - 7.18 (m, 4H), 6.07 (q, J = 7.2 Hz, 1H), 3.88 (s, 3H), 2.01 (d, J = 7.1 Hz, 3H). 13 C NMR (100 MHz, CDC13) d (ppm) 146.0, 139.7, 130.0, 126.6, 125.8, 125.6, 123.5, 120.4, 120.3, 119.4, 119.2, 110.6, 110.0, 52.2, 52.2, 17.4. HRMS (ESI): m / z [M + H] + calcd. for C 22 H 20 NO2 + : 330.1489, found 330.1497.

[0089] Example 14

[0090]

[0091] Compound 3an was prepared as follows:

[0092] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene la (0.20 mmol), Hanstzch ester 2n (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5 W blue LED. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3an. Target product 28.0 mg, 51% yield.

[0093] 1 H NMR (400 MHz, CDC13) d (ppm) 7.94 (d, J = 8.0 Hz, 2H), 7.65-7.62 (m, 1H), 7.30 (d, J = 4.0 Hz, 1H), 7.17-7.07 (m, 5H), 6.59 (d, J = 4.0 Hz, 1H), 5.70 (q, J = 8.0 Hz, 1H), 3.88 (s, 3H), 1.94 (d, J = 8.0 Hz, 3H). 13 C NMR (100 MHz, CDC13) d (ppm) 166.7, 147.9, 136.0, 130.1, 129.3, 128.8, 125.9, 124.7, 121.7, 121.0, 119.8, 110.0, 101.9, 54.7, 52.1, 21.7. HRMS (ESI): m / z [M + H] + calcd. for C 18 H 18 NO2 + : 280.1332, found 280.1320.

[0094] Example 15

[0095]

[0096] The compound 3bb was prepared as follows:

[0097] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene 1a (0.20 mmol), Hanstzch ester 2a (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature under a 5W blue LED for 24 h. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3aa. Target product 28.6 mg, 74% yield.

[0098] 1 H NMR (400 MHz, CDC13) δ (ppm) 7.56 (d, J = 8.0, Hz, 2H), 7.35-7.21 (m, 6H), 7.16 (d, J = 8.0, Hz, 2H), 4.03 (s, 2H). 13 C NMR (100 MHz, CDC13) δ (ppm) 146.8, 139.4, 132.3, 129.7, 129.0, 128.8, 126.7, 119.0, 110.0, 42.0. HRMS (ESI): m / z [M + Na] + calcd. for C 14 H 11 NNa + : 216.0784, found 216.0768.

[0099] Example 16

[0100]

[0101] The compound 3cb was prepared as follows:

[0102] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene 1c (0.20 mmol), Hanstzch ester 2b (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature under a 5W blue LED for 24 h. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3cb. Target product 45.0 mg, 91% yield.

[0103] 1H NMR (400 MHz, CDC13) δ (ppm) 7.85 (d, J = 8.0 Hz, 2H), 7.38 (d, J = 8.1 Hz, 2H), 7.32 (t, J = 7.4 Hz, 2H), 7.26-7.22 (m, 1H), 7.17 (d, J = 4.0 Hz, 2H), 4.07 (s, 2H), 3.03 (s, 3H). 13 CNMR (100 MHz, CDC13) δ (ppm) 147.7, 139.4, 138.3, 129.8, 129.0, 128.8, 127.6, 126.7, 44.6, 41.8. HRMS (ESI): m / z [M+Na] + calcd. for C 14 H 14 Na02S + : 269.0607, found: 269.0600.

[0104] Example 17

[0105]

[0106] Compound 3db was prepared as follows:

[0107] In an argon-filled glove box, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene Id (0.20 mmol), Hanstzch ester 2b (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5W blue LED. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3db. Target product 36.0 mg, 85% yield.

[0108] 1 H NMR (400 MHz, CDC13) δ (ppm) 7.88 (d, J = 8.0 Hz, 2H), 7.30-7.16 (m, 7H), 4.03 (s, 2H), 2.57 (s, 3H). 13 CNMR (100 MHz, CDC13) δ (ppm) 197.8, 146.8, 140.0, 135.3, 129.1, 128.9, 128.6, 126.4, 41.9, 26.6. HRMS (ESI): m / z [M+H] + calcd. for C 15 H 15O + :211.1117,found211.1119.

[0109] Example 18

[0110]

[0111] The preparation method of compound 3eb is as follows:

[0112] In an argon-filled glove box, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 minutes, 4CzIPN (0.004 mmol, 3.2 mg), bromoaryl 1e (0.20 mmol), Hanstzsch ester 2b (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature under a 5 W blue LED for 24 hours. The mixture was then concentrated in vacuo, and the residue was purified by silica gel flash column chromatography to obtain the desired product 3eb. 31.5 mg of the desired product was obtained in an 80% yield.

[0113] 1 H NMR (400MHz, CDCl3) δ (ppm) 9.97 (s, 1H), 7.80 (d, J = 8.0Hz, 2H), 7.36-7.27 (m, 4H), 7.25-7.20 (m, 1H), 7.18 (d, J = 8.0Hz, 2H), 4.05 (s, 2H). 13 C NMR (100MHz, CDCl3) δ (ppm) 192.0, 148.4, 140.0, 134.7, 130.1, 129.6, 129.0, 128.7, 126.5, 42.1. HRMS (ESI): m / z [M+H] + calcd.for C 14 H 13 O + :197.0961,found 197.0970.

[0114] Example 19

[0115]

[0116] The preparation method of compound 3fb is as follows:

[0117] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene If (0.20 mmol), Hanstzch ester 2b (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature under a 5W blue LED for 24 h. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3fb. Target product 30.5 mg, 62% yield.

[0118] 1 H NMR (400 MHz, CDC13) δ (ppm) 7.56 (d, J = 8.0 Hz, 2H), 7.51 (d, J = 8.0 Hz, 2H), 7.41 (t, J = 8.0 Hz, 2H), 7.33-7.21 (m, 8H), 4.02 (s, 2H). 13 C NMR (100 MHz, CDC13) δ (ppm) 141.0, 140.3, 139.1, 129.3, 129.0, 128.7, 128.5, 127.2, 127.1, 127.0, 126.2, 41.6. HRMS (APCI): m / z [M] + calcd. for C 19 H 16 + : 244.1247, found: 244.1248.

[0119] Example 20

[0120]

[0121] The compound 3gb was prepared as follows:

[0122] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene Ig (0.20 mmol), Hanstzch ester 2b (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature under a 5W blue LED for 24 h. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3gb. Target product 22.6 mg, 57% yield.

[0123] 1 H NMR (400 MHz, CDC13) δ (ppm) 7.30-7.26 (m, 2H), 7.22-7.18 (m, 4H), 6.78 (d, J = 8.0 Hz, 1H), 6.75-6.74 (m, 1H), 6.73 (s, 1H), 3.95 (s, 2H), 3.76 (s, 3H). 13 C NMR (100 MHz, CDC13) δ (ppm) 159.7, 142.7, 140.9, 129.4, 128.9, 128.5, 126.1, 121.4, 114.8, 111.3, 55.2, 42.0. HRMS (ESI): m / z [M+H] + calcd. for C 14 H 15 O + : 199.1117, found: 199.1122.

[0124] Example 21

[0125]

[0126] Compound 3hb was prepared as follows:

[0127] In an argon-filled glove box, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene 1h (0.20 mmol), Hanstzch ester 2b (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5W blue LED. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3hb. Target product 38.0 mg, 84% yield.

[0128] 1 H NMR (400 MHz, CDC13) δ (ppm) 7.89 (d, J = 8.0 Hz, 1H), 7.42 (t, J = 8.0 Hz, 1H), 7.29-7.13 (m, 7H), 4.38 (s, 2H), 3.81 (s, 3H). 13 C NMR (100 MHz, CDC13) δ (ppm) 142.2, 140.9, 132.0, 131.6, 130.7, 130.0, 128.9, 128.3, 126.3, 126.0, 52.0, 39.6. HRMS (ESI): m / z [M+H]+ calcd. for C 15 H 15 O2 + : 227.1067, found: 227.1074.

[0129] Example 22

[0130]

[0131] Compound 3ib was prepared as follows:

[0132] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene li (0.20 mmol), Hanstzch ester 2b (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5 W blue LED. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3ib. Target product 30.0 mg, 66% yield.

[0133] 1 H NMR (400 MHz, CDC13) δ (ppm) 7.30-7.25 (m, 2H), 7.21-7.17 (m, 3H), 6.35-6.31 (m, 3H), 3.91 (s, 2H), 3.75 (s, 6H). 13 C NMR (100 MHz, CDC13) δ (ppm) 160.8, 143.4, 140.7, 128.9, 128.5, 126.2, 107.1, 98.0, 55.3, 42.2. HRMS (ESI): m / z [M+H] + calcd. for C 15 H 17 O2 + : 229.1223, found 229.1233.

[0134] Example 23

[0135]

[0136] Compound 3jb was prepared as follows:

[0137] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene 1j (0.20 mmol), Hanstzch ester 2b (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature under a 5W blue LED for 24 h. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3jb. Target product 32.5 mg, 72% yield.

[0138] 1 H NMR (400 MHz, CDC13) δ (ppm) 10.37 (s, 2H), 8.16 (d, J = 7.6 Hz, 2H), 7.62 (t, J = 7.7 Hz, 1H), 7.31-7.23 (m, 2H), 7.18 (t, J = 7.3 Hz, 1H), 7.04 (d, J = 7.4 Hz, 2H), 4.95 (s, 2H). 13 C NMR (100 MHz, CDC13) δ (ppm) 191.1, 136.11, 135.5, 128.8, 128.2, 127.8, 126.6, 31.3. HRMS (ESI): m / z [M + Na] + calcd. for C 15 H 12 NaO2 + : 247.0730, found 247.0766.

[0139] Example 24

[0140]

[0141] The compound 3kb was prepared as follows:

[0142] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene 1j (0.20 mmol), Hanstzch ester 2b (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature under a 5W blue LED for 24 h. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3jb. Target product 32.5 mg, 72% yield.

[0143] 1 H NMR (400 MHz, CDC13) δ (ppm) 10.19 (s, 1H), 7.88 (dd, J = 8.0, 6.0 Hz, 1H), 7.32-7.28 (m, 2H), 7.25-7.20 (m, 1H), 7.15 (d, J = 8.0 Hz, 2H), 7.08 (td, J = 8.0, 2.5 Hz, 1H), 6.92 (dd, J = 8.0, 2.5 Hz, 1H), 4.44 (s, 2H). 13 C NMR (100 MHz, CDC13) δ (ppm) 190.7, 167.2, 164.6, 146.7 (d, J = 9.0 Hz), 139.3, 135.0 (d, J = 10.0 Hz), 130.5, 128.8 (d, J = 11.0 Hz), 126.7, 118.5 (d, J = 22.0 Hz), 114.2 (d, J = 22.0 Hz), 37.9. 19 F NMR (376 MHz, CDC13) δ (ppm) -103.21. HRMS (ESI): m / z [M+Na] + calcd. for C 14 H 11 FNaO + : 237.0686, found 237.0689.

[0144] Example 25

[0145]

[0146] The compound 3lb was prepared as follows:

[0147] In an argon-filled glove box, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene 1l (0.20 mmol), Hanstzch ester 2b (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5W blue LED. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3lb. Target product 29.0 mg, 66% yield.

[0148] 1H NMR (400 MHz, CDCI3) δ (ppm) 7.80-7.74 (m, 3H), 7.63 (s, 1 H), 7.46-7.37 (m, 2H), 7.32-7.26 (m, 3H), 7.22-7.18 (m, 3H), 4.14 (s, 2H). 13 C NMR (100 MHz, CDCI3) δ (ppm) 141.0, 138.6, 133.6, 132.1, 129.0, 128.5, 128.1, 127.7, 127.6, 127.6, 127.1, 126.2, 126.0, 125.4, 42.1. HRMS (APCI): m / z [M+H] + calcd. for C 17 H 14 + : 218.1090, found: 218.1115.

[0149] Example 26

[0150]

[0151] Compound 3mb was prepared as follows:

[0152] In an argon-filled glove box, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene 1m (0.20 mmol), Hanstzch ester 2b (0.30 mmol), zinc bromide (0.40 mmol) and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5W blue LED. Then, the mixture was concentrated in vacuo and the residue was purified by flash column chromatography on silica gel to give the desired product 3mb. 37.0 mg, 82% yield.

[0153] 1 H NMR (400 MHz, CDCI3) δ (ppm) 8.96 (s, 1 H), 7.97 (s, 1 H), 7.85 (d, J = 8.2 Hz, 1 H), 7.32-7.19 (m, 6H), 4.15 (s, 2H). 13 C NMR (100 MHz, CDCI3) δ (ppm) 154.2, 153.7, 140.8, 139.8, 131.4, 129.0, 128.6, 127.0, 126.3, 123.6, 121.7, 41.9. HRMS (ESI): m / z [M+H] + calcd. for C14 H 12 NS + :226.0685, found 226.0684.

[0154] Example 27

[0155]

[0156] Compound 3nb was prepared as follows:

[0157] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene In (0.20 mmol), Hanstzch ester 2b (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5 W blue LED. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3nb. Target product 54.0 mg, 56% yield.

[0158] 1 H NMR (400 MHz, CDC13) d (ppm) 7.96 (d, J = 8.0 Hz, 2H), 7.31 - 7.16 (m, 7H), 5.45 (d, J = 4.0 Hz, 1H), 4.85 (td, J = 8.0, 4.0 Hz, 1H), 4.03 (s, 2H), 2.52 - 2.41 (m, 3H), 2.10 (dt, J = 22.8, 9.0 Hz, 2H), 2.03 - 1.81 (m, 3H), 1.80 - 1.59 (m, 5H), 1.59 - 1.39 (m, 2H), 1.37 - 1.16 (m, 4H), 1.09 (s, 4H), 0.90 (s, 3H). 13 C NMR (100 MHz, CDC13) d (ppm) 165.9, 146.4, 140.2, 140.0, 129.8, 128.9, 128.9, 128.7, 128.6, 126.4, 122.0, 74.2, 51.7, 50.2, 47.6, 41.9, 38.2, 37.0, 36.8, 35.9, 31.5, 31.4, 30.8, 27.8, 21.9, 20.4, 19.4, 13.6.

[0159] Example 28

[0160]

[0161] Compound 3oh was prepared as follows:

[0162] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene 1o (0.20 mmol), Hanstzch ester 2h (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5 W blue LED. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3oh. 49.0 mg, 92% yield.

[0163] 1 H NMR (400 MHz, CDC13) d (ppm) 7.53 (d, J = 8.0 Hz, 2H), 7.27 (d, J = 7.9 Hz, 2H), 6.74 (d, J = 7.7 Hz, 1H), 6.64 (m, 2H), 5.92 (s, 2H), 3.93 (s, 2H). 13 C NMR (100 MHz, CDC13) d (ppm) 147.9, 146.2, 145.4, 133.8, 129.1, 128.5 (q, J = 33.0 Hz), 125.4 (q, J = 4.0 Hz), 124.3 (q, J = 270.0 Hz), 109.4, 108.3, 101.0, 41.4. 19 F NMR (376 MHz, CDC13) d (ppm) -62.3. HRMS (APCI) m / z [M] + calcd. for C 15 H 11 F3O2 + : 280.0711, found 280.0723.

[0164] Example 29

[0165]

[0166] Compound 3pb was prepared as follows:

[0167] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene Ip (0.20 mmol), Hanstzch ester 2h (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5 W blue LED. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3ph. Target product 36.3 mg, 78% yield.

[0168] 1 H NMR (400 MHz, CDC13) δ (ppm) 7.13-7.10 (m, 2H), 6.98-6.94 (m, 2H), 6.74-6.72 (m, 1H), 6.64-6.62 (m, 2H), 5.91 (s, 2H), 3.85 (s, 2H). 13 C NMR (100 MHz, CDC13) δ (ppm) 162.7, 160.2, 147.8, 146.0, 136.9 (d, J = 3.0 Hz), 134.8, 130.1 (d, J = 8.0 Hz), 121.7, 115.2 (d, J = 21.0 Hz), 109.3, 108.2, 100.9, 40.8. 19 F NMR (376 MHz, CDC13) δ (ppm) -117.35. HRMS (APCI): m / z [M] + calcd. for C 14 H 11 FO2 + : 230.0738, found 230.0729.

[0169] Example 30

[0170]

[0171] Compound 3qb was prepared as follows:

[0172] In an argon-filled glovebox, cobalt iodide (0.03 mmol, 9.6 mg) was dissolved in MeCN (2.0 mL) in a 10 mL vial. After stirring for 15 min, 4CzIPN (0.004 mmol, 3.2 mg), bromoarene 1q (0.20 mmol), Hanstzch ester 2h (0.30 mmol), zinc bromide (0.40 mmol), and DIPEA (0.50 mmol) were added to the solution. The reaction was stirred at room temperature for 24 h under a 5 W blue LED. Then, the mixture was concentrated in vacuo, and the residue was purified by flash column chromatography on silica gel to give the desired product 3qh. 37.0 mg, 75% yield.

[0173] 1 H NMR (400 MHz, CDC13) δ (ppm) 7.24 (d, J = 8.0 Hz, 2H), 7.09 (d, J = 8.0 Hz, 2H), 6.73 (d, J = 8.0 Hz, 1H), 6.63-6.61 (m, 2H), 5.91 (s, 2H), 3.84 (s, 2H). 13 C NMR (100 MHz, CDC13) δ (ppm) 147.8, 146.0, 139.7, 134.4, 131.9, 130.1, 128.6, 121.7, 109.3, 108.2, 100.9, 40.9. HRMS (APCI): m / z [M] + calcd. for C 14 H 11 ClO2 + :246.0442, found 246.0450.

[0174] The above description is only the preferred embodiment of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for the photo / cobalt redox catalytic coupling reaction of aryl halides and hans esters, characterized in that: A photocatalyst and a cobalt salt are added to a solvent containing an organic amine and a zinc salt, and under visible light irradiation, the coupling reaction of an aryl halide and a Hans ester is catalyzed to synthesize diphenylmethane compounds and their derivatives; The aryl halide is a compound represented by formula 1, Wherein, Ar is a benzene ring, a naphthalene ring or an aromatic heterocycle substituted with one of ketocarbonyl, aldehyde, cyano, phenyl, trifluoromethyl, fluorine, chlorine and hydrogen, and X is Br or I; The hans ester is a compound represented by formula 2, Wherein, R is one of benzyl, halogenated benzyl, alkyl or alkoxy substituted benzyl, carbazolyl, and indolyl.

2. The method for the light / cobalt redox catalyzed coupling reaction of aryl halides and hans esters according to claim 1, characterized in that: The cobalt salt is selected from at least one of cobalt fluoride, cobalt chloride, cobalt bromide, cobalt iodide, cobalt acetate, cobalt acetylacetonate, cobalt isooctanoate, and cobalt hypochlorite, and the amount used is 0.0002-0.30 equivalents.

3. The method for the light / cobalt redox catalyzed coupling reaction of aryl halides and hans esters according to claim 1, characterized in that: The photocatalyst is a CzIPN catalyst or a CzIPN derivative catalyst, and the dosage is 0.0001-0.2 equivalents.

4. The method for the light / cobalt redox catalyzed coupling reaction of aryl halides and hans esters according to claim 1, characterized in that: The organic amine is at least one of methylamine, diethylamine, triethylamine, N,N-diisopropylethylamine, tetramethylethylenediamine, and triethylenediamine, and the amount used is 0.5-8 equivalents.

5. The method for the light / cobalt redox catalyzed coupling reaction of aryl halides and hans esters according to claim 1, characterized in that: The zinc salt is selected from at least one of zinc sulfate, zinc carbonate, zinc oxide, zinc sulfide, zinc bromide, zinc acetate, zinc stearate, and zinc lactate.

6. The method for the light / cobalt redox catalyzed coupling reaction of aryl halides and hans esters according to claim 1, characterized in that: The solvent is at least one of a nitrile solvent, a halogenated alkane solvent, an amide solvent, a sulfoxide solvent or water.

7. The method for the light / cobalt redox catalyzed coupling reaction of aryl halides and hans esters according to claim 1, characterized in that: The solvent is selected from at least one of acetonitrile, water, dichloromethane, chloroform, 1,2-dichloroethane, N,N-dimethylformamide, N,N-dimethylacetamide or dimethyl sulfoxide.

8. The method for the light / cobalt redox catalyzed coupling reaction of aryl halides and hans esters according to claim 1, characterized in that: The wavelength of the visible light is 360-500 nm.

9. The method for the light / cobalt redox catalyzed coupling reaction of aryl halides and hans esters according to claim 1, characterized in that: The reaction temperature of the coupling reaction is 15-50° C., and the reaction time is 12-36 hours.

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