A method for preparing a beta-boryl substituted aldehyde derivative

Abstract

The present application relates to a kind of preparation of beta-boron group substituted aldehyde derivative method. Specifically under the condition of copper catalysis, diboron compound, olefin, carbon monoxide are prepared by one-pot method to obtain beta-boron group substituted aldehyde derivative. The present application is obtained from simple and readily available raw materials and catalyst, and a series of beta-boron group substituted aldehyde derivatives are obtained by carbonylation reaction.

Description

Technical Field

[0001] This invention relates to a method for synthesizing β-boron-substituted aldehyde derivatives. Background Technology

[0002] β-Boron-substituted aldehyde derivatives are an important class of aldehyde derivatives, widely found in natural products and pharmaceuticals, and possess biological and insecticidal activities. In addition, they are also an important component of organic synthesis and functional materials.

[0003] Traditional synthesis of these compounds requires stoichiometric coupling reagents, which greatly limits their synthetic applications. Furthermore, the regioselectivity and stereoselectivity of the products are also significant factors limiting their development.

[0004] To date, there have been no reports on one-step synthesis of β-boron-substituted aldehyde derivatives. Traditional multi-step synthesis methods are cumbersome. This invention aims to prepare β-boron-substituted aldehyde derivatives through direct regio and stereoselectivity of olefins, diboron compounds, and the bulk chemical carbon monoxide.

[0005] In summary, this paper describes an efficient, atom-economical, and regioselective method for the preparation of β-boron-substituted aldehyde derivatives. Summary of the Invention

[0006] The purpose of this invention is to provide a method for synthesizing β-boron-substituted aldehyde compounds.

[0007]

[0008] Reaction Equation 1: Synthesis of β-Boron-substituted Aldehyde Derivatives

[0009] The specific operating steps are as follows (reaction equation 1):

[0010] The reaction is carried out in a reactor. First, a catalyst, ligand, base, alcohol, olefin 1, diboron compound 2 and solvent are added. Then, the atmosphere in the reactor is replaced with carbon monoxide gas 3. After replacement, carbon monoxide gas at 5-50 bar is introduced and the reaction is carried out at 50-120°C, preferably 70-100°C. The reaction time is 28-36 hours, preferably 20-24 hours. After the reaction is completed, β-boron-substituted aldehyde 4 is obtained by column chromatography.

[0011] The amount of olefin 1 used is 0.1-10 mmol, preferably 0.2 mmol.

[0012] The amount of diboron compound 2 used is 0.15-15 mmol, preferably 0.3 mmol.

[0013] The catalyst is one or more of cuprous chloride, copper acetate, copper bromide, and copper carbene complex, preferably copper chloride; the amount of catalyst used is 1-10 mol% of the amount of olefin 1, preferably 5 mol%.

[0014] The ligand is one or more of the following: triphenylphosphine, 1,2-bis(diphenylphosphine)ethane, 1,1'-bis(diphenylphosphine)ferrocene, 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene, 2-methylene-1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-imidazolium, and 2-methylene-1,3-bis(2,4,6-trimethylphenyl)imidazolium; the amount of ligand used is 1-10 mol% of the amount of olefin 1, preferably 5 mol.

[0015] The base is one or more of potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, sodium methoxide, potassium methoxide, and sodium ethoxide, preferably potassium tert-butoxide; the amount of base used is 100-400 mol% of the amount of olefin 1, preferably 300 mol%.

[0016] The alcohol is one or more of tert-butanol, methanol, ethanol, and butanol, preferably p-tert-butanol; the amount of alcohol used is 100-400 mol% of the amount of olefin 1, preferably 200 mol%.

[0017] The solvent is one or more of n-hexane, tetrahydrofuran, toluene, diethyl ether, methyl tert-butyl ether, 1,4-dioxane, and 1,2-dichloroethane, preferably tetrahydrofuran; the amount of solvent used is 1.0-10.0 mL per millimole of olefin, preferably 5.0 mL.

[0018] The present invention has the following advantages:

[0019] This invention synthesizes a series of β-boron-substituted aldehyde compounds through copper-catalyzed olefin borylation and carbonylation.

[0020] First, the reaction exhibits high regioselectivity. Second, this reaction is direct and efficient, demonstrating economical reaction steps. Finally, the reaction system exhibits good functional group compatibility, enabling the one-step construction of β-boron-substituted aldehyde compounds containing quaternary carbon centers. Detailed Implementation

[0021] To better understand the present invention, the following examples are provided. The reaction materials and results of Examples 1-10 are shown in Table 1.

[0022] Table 1. Reaction results of different substituted alkenes

[0023]

[0024]

[0025]

[0026]

[0027] Example 1

[0028] The reaction was carried out in a reactor. First, 0.01 mmol of cuprous chloride catalyst (5 mol% of olefin 1a), 0.01 mmol of 2-methylene-1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-imidazolium ligand (5 mol% of olefin 1a), potassium tert-butoxide (300 mol% of olefin 1a), olefin 1a (0.2 mmol), bis-pinacol boronic acid ester 2 (0.3 mmol), tert-butanol (0.4 mmol), and tetrahydrofuran solvent (1.0 mL) were added. The total charge in the reactor was 10% of its volume. Then, carbon monoxide gas was added and purged three times, followed by a final purging of 5 bar of carbon monoxide gas. The reaction was carried out at 80 °C for 24 hours. After the reaction, compound 4a was obtained by column chromatography in 63% yield. The structure of the compound was identified by NMR (1H, 1C, and 1H NMR) and high-resolution mass spectrometry.

[0029] The test data is as follows:

[0030] 2-Methyl-2-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanal(4a): 34.5mg, 63% yield, yellow oil.Eluent: pentane / ethyl acetate=50 / 1-20 / 1. 1 H NMR (700MHz, CDCl3) δ9.51 (s, 1H), 7.34 (t, J = 7.7Hz, 2H), 7.29 (d, J = 7.9Hz, 2H), 7.25 (dd, J = 13.1, 5.8Hz,1H),1.57(s,3H),1.44(d,J=15.5Hz,1H),1.34(d,J=15.5Hz,1H),1.13(s,6H),1.12(s,6H).

[0031] 13 C NMR (176MHz, CDCl3) δ202.47,202.45,141.7,128.6,127.0,83.2,52.0,24.7,24.6,21.5.

[0032] 11 B NMR (128MHz, CDCl3) δ 33.31.

[0033] HRMS(ESI-FT-ICR)m / z:[M+Na] + Calcd for C 16 H 23 BO3Na 297.1635; Found:297.1643.

[0034] Example 2

[0035] The operation process and conditions were the same as in Example 1, except that the yield of raw material 1, 4b was 57% as shown in Table 1. The structure of the compound was identified by NMR (H1N, C1N, and BON) and high-resolution mass spectrometry.

[0036] 2-Methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-(p-tolyl)propanal(4b)

[0037] 32.8mg, 57% yield, slight yellow oil.Eluent: pentane / ethyl acetate=50 / 1-20 / 1. 1 H NMR (700MHz, CDCl3) δ9.47(s,1H),7.16(q,J=8.3Hz,4H),2.32(s,3H),1.55(s,3H),1.36(dd,J=40.2,15.5Hz,2H),1.15(s,5H),1.14(s,6H). 13 C NMR (176MHz, CDCl3) δ202.52,202.51,138.6,136.7,129.3,126.9,83.2,51.7,24.7,24.7,21.5,20.9.

[0038] 11 B NMR (128MHz, CDCl3) δ 33.79.

[0039] HRMS(ESI-FT-ICR)m / z:[M+Na] + Calcd for C 17 H 25 BO3Na 311.1792;Found:311.1799.

[0040] Example 3

[0041] The operation process and conditions were the same as in Example 1, except that the yield of raw material 1 in Table 1 was 56%, and the structure of the compound was identified by NMR (H1N, C1N, and BON) and high-resolution mass spectrometry.

[0042] 2-(4-(tert-Butyl)phenyl)-2-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanal(4c)

[0043] 37.0mg, 56% yield, yellow oil.Eluent: pentane / ethyl acetate=50 / 1-20 / 1.

[0044] 1 H NMR (400MHz, CDCl3) δ9.49 (s, 1H), 7.36 (d, J = 8.3Hz, 2H), 7.21 (d, J = 8.2Hz, 2H ),1.56(s,3H),1.38(d,J=25.6Hz,2H),1.30(s,9H),1.13(s,6H),1.11(s,6H).

[0045] 13 C NMR (101MHz, CDCl3) δ202.6,149.9,138.5,126.7,125.5,83.2,51.6,34.4,31.3,24.7,24.6,21.3.

[0046] 11 B NMR (128MHz, CDCl3) δ 33.44.

[0047] HRMS(ESI-FT-ICR)m / z:[M+Na] + Calcd for C 20 H 31 BO3Na 353.2262; Found:353.2261.

[0048] Example 4

[0049] The operation process and conditions were the same as in Example 1, except that the raw material 1 in Table 1 had a yield of 55% after 4 days. The structure of the compound was identified by NMR (H1N, C1N, and BON) and high-resolution mass spectrometry.

[0050] 2-(4-Methoxyphenyl)-2-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanal(4d)

[0051] 33.4mg, 55% yield, colorless oil.Eluent: pentane / ethyl acetate=20 / 1-10 / 1.

[0052] 1 H NMR (700MHz, CDCl3) δ9.44 (s, 1H), 7.20 (d, J = 8.8Hz, 2H), 6.88 (d, J = 8.8Hz, 2H), 3.7 9(s,3H),1.54(s,3H),1.41(d,J=15.5Hz,1H),1.31(d,J=15.5Hz,1H),1.14(s,12H).

[0053] 13 C NMR (176MHz, CDCl3) δ202.4,158.6,133.5,128.2,114.0,83.2,55.3,51.3,24.7,24.7,21.5.

[0054] 11 B NMR (128MHz, CDCl3) δ 33.37.

[0055] HRMS(ESI-FT-ICR)m / z:[M+Na] + Calcd for C 17 H 25 BO4Na 327.1741;Found:327.1739.

[0056] Example 5

[0057] The operation process and conditions were the same as in Example 1, except that the yield of raw material 1, 4e was 48% as shown in Table 1. The structure of the compound was identified by NMR (H1N, C1N, fluorine and boron spectra) and high-resolution mass spectrometry.

[0058] 2-(4-Fluorophenyl)-2-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanal(4e)

[0059] 28.0mg, 48% yield, colorless oil.Eluent: pentane / ethyl acetate=50 / 1-20 / 1.

[0060] 1H NMR (700MHz, CDCl3) δ9.47(s,1H),7.25(dd,J=8.5,5.7Hz,2H),7.03(t,J=8.5Hz,2H),1.56(s,3H),1.37(dd,J=83.4,15.5Hz,2H),1.13(s,12H).

[0061] 13 C NMR (176MHz, CDCl3) δ202.1, 161.9 (d, J = 246.2Hz), 137.3, 128.7 (d, J = 8.0Hz), 115.4 (d, J = 21.1Hz), 83.3, 51.4, 24.7, 24.6, 21.6.

[0062] 19 F NMR (376MHz, CDCl3) δ -115.92.

[0063] 11 B NMR (128MHz, CDCl3) δ 33.44.

[0064] HRMS(ESI-FT-ICR)m / z:[M+Na] + Calcd for C 16 H 22 BFO3Na 315.1541; Found:315.1548.

[0065] Example 6

[0066] The operation process and conditions were the same as in Example 1, except that the yield of raw material 1 was 55% as shown in Table 1. The structure of the compound was identified by NMR (H1N, C1N, and BON) and high-resolution mass spectrometry.

[0067] 2-Methyl-2-(naphthalen-1-yl)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanal(4f)

[0068] 35.6mg, 55% yield, pale yellow oil.Eluent: pentane / ethyl acetate=50 / 1-20 / 1. 1H NMR(400MHz, CDCl3)δ9.74(s,1H),7.92–7.71(m,3H),7.65–7.57(m,1H),7.51–7.41(m,3H) ),1.75(s,3H),1.69(d,J=15.5Hz,1H),1.48(d,J=15.5Hz,1H),1.15(s,6H),1.10(s,6H).

[0069] 13 C NMR (101MHz, CDCl3) δ205.7,138.5,134.6,131.3,129.4,128.7,126.4,125.4,125.2,124.7,83.2,53.0,24.8,24.7,23.3.

[0070] 11 B NMR (128MHz, CDCl3) δ 33.11.

[0071] HRMS(ESI-FT-ICR)m / z:[M+Na] + Calcd for C 20 H 25 BO3Na 347.1792;Found:347.1799.

[0072] Example 7

[0073] The operation process and conditions were the same as in Example 1, except that the raw material 1 in Table 1 had a yield of 53% (4g). The structure of the compound was identified by NMR (H1N, C1N, and BON spectra) and high-resolution mass spectrometry.

[0074] 2-(3,5-Dimethylphenyl)-2-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanal(4g)

[0075] 32.1mg, 53% yield, colorless oil.Eluent: pentane / ethyl acetate=50 / 1-20 / 1.

[0076] 1 H NMR (700MHz, CDCl3) δ9.47 (s, 1H), 6.88 (s, 3H), 2.30 (s, 6H), 1.54 (s, 3H), 1.35 (dd, J = 36.5, 15.5Hz, 2H), 1.15 (s, 6H), 1.15 (s, 6H).

[0077] 13 C NMR (176MHz, CDCl3) δ202.7,202.6,141.6,138.1,128.6,124.8,83.2,51.9,24.7,24.7,21.6,21.4.

[0078] 11 B NMR (128MHz, CDCl3) δ 33.57.

[0079] HRMS(ESI-FT-ICR)m / z:[M+Na] + Calcd for C 18 H 27 BO3Na 325.1948;Found:325.1947.

[0080] Example 8

[0081] The operation process and conditions were the same as in Example 1, except that the raw material 1 in Table 1 had a yield of 65% after 4 hours. The structure of the compound was identified by NMR (H1N, C1N, and BON spectra) and high-resolution mass spectrometry.

[0082] 1-((4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)-1,2,3,4-tetrahydronaphthalene-1-carbaldehyde(4h)

[0083] 39.0mg, 65% yield, colorless oil.Eluent: pentane / ethyl acetate=50 / 1-20 / 1.

[0084] 1 H NMR(400MHz, CDCl3)δ9.49(s,1H),7.22–7.02(m,4H),2.90–2.69(m,2H),2.18–2.05(m,2H), 1.95–1.74(m,2H),1.43(d,J=15.4Hz,1H),1.23(d,J=10.9Hz,1H),1.12(s,6H),1.09(s,6H).

[0085] 13 C NMR (101MHz, CDCl3) δ202.5,138.3,136.40,129.5,128.7,126.8,126.2,83.1,51.76,23.0,29.6,24.7,24.6,19.6.

[0086] 11 B NMR (128MHz, CDCl3) δ 32.99.

[0087] HRMS(ESI-FT-ICR)m / z:[M+H] + Calcd for C 18 H 26 BO3 301.1972; Found:301.1973.

[0088] Example 9

[0089] The operation process and conditions were the same as in Example 1, except that the yield of raw material 1,4i was 58% as shown in Table 1. The structure of the compound was identified by NMR (H1N, C1N, and BON) and high-resolution mass spectrometry.

[0090] 2-Phenyl-2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)butanal(4i)

[0091] 33.4mg, 58% yield, pale yellow oil.Eluent: pentane / ethyl acetate=50 / 1-20 / 1. 1 H NMR(400MHz, CDCl3)δ9.62(s,1H),7.41–7.31(m,2H),7.25(m,3H),2.17–1.91( m,2H),1.43(q,J=15.7Hz,2H),1.14(s,6H),1.12(s,6H),0.76(t,J=7.4Hz,3H).

[0092] 13 C NMR (101MHz, CDCl3) δ203.52,140.50,128.50,127.51,126.90,83.29,55.91,28.26,24.67,8.51.

[0093] 11 B NMR (128MHz, CDCl3) δ 33.28.

[0094] HRMS(ESI-FT-ICR)m / z:[M+Na] + Calcd for C 17 H 25 BO3Na 311.1792;Found:311.1797.

[0095] Example 10

[0096] The operation process and conditions were the same as in Example 1, except that the yield of raw material 1,4j was 40% as shown in Table 1. The structure of the compound was identified by NMR (H1N, C1N, and BON) and high-resolution mass spectrometry.

[0097] 2-Cyclohexyl-2-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanal(4j)

[0098] 27.3mg, 40% yield, colorless oil.Eluent: pentane / ethyl acetate=50 / 1-20 / 1.

[0099] 1 H NMR(400MHz, CDCl3)δ9.88(s,1H),7.38–7.28(m,2H),7.24(m,3H),2.03(t,J= 11.9Hz,1H),1.80–1.60(m,4H),1.52–1.21(m,8H),1.13(s,6H),1.07(s,6H).

[0100] 13 C NMR (101MHz, CDCl3) δ205.1,140.3,128.1,128.1,126.6,100.0,83.3,59.0,44.9,28.6,28.1,26.9,26.5,24.7,24.5.

[0101] 11 B NMR (128MHz, CDCl3) δ 33.48.

[0102] HRMS(ESI-FT-ICR)m / z:[M+Na] + Calcd for C 21 H 31 BO3Na 365.2262; Found:365.2275.

[0103] Product Application Examples

[0104] Compound 4a (54.8 mg), iodobenzene (45 mg), potassium carbonate (41.4 mg), Pd(PPh3)4 (2.4 mg), N,N-dimethylformamide (3.0 mL), and water (0.45 mL) were added to a flask, and the mixture was then degassed three times with nitrogen. The reaction was carried out at 80 °C for 3 hours. After the reaction was completed, a colorless oily product 5 (33.2 mg) was isolated, with a yield of 74%. The structure of compound 5 was identified by NMR (1H and 1C) and high-resolution mass spectrometry. 1 H NMR (400MHz, CDCl3) δ9.63 (s, 1H), 7.34 (ddd, J = 18.4, 7.9, 6.4Hz, 3H), 7.16 (m, 5H), 6.79 (dd, J = 6.4, 3.0Hz, 2H), 3.20 (q, J = 13.6Hz, 2H), 1.38 (s, 3H).

[0105] 13 C NMR (101MHz, CDCl3) δ202.0,139.3,136.8,130.4,128.8,127.8,127.6,127.4,126.4,55.1,42.7,18.2.

[0106] HRMS(ESI-FT-ICR)m / z:[M+Na] + Calcd for C 16 H 16 ONa 247.1093;Found:247.1099.

[0107] Comparative Example 1

[0108] The reaction process and conditions were the same as those in Example 1, except that when the carbon monoxide gas pressure was changed to 3 bar (gauge pressure), the yield of the product in Example 1 was 51%.

[0109] Comparative Example 2

[0110] The reaction process and conditions were the same as in Example 1, except that the yield of the product in Example 1 was 17% when the carbon monoxide gas pressure was 55 bar (gauge pressure).

[0111] Comparative Example 3

[0112] The reaction process and conditions were the same as those in Example 1, except that when the reaction temperature was changed to 40°C, the yield of the product in Example 1 was 36%.

[0113] Comparative Example 4

[0114] The reaction process and conditions were the same as those in Example 1, except that the yield of the product in Example 1 was 47% when the reaction temperature was 130°C.

[0115] Comparative Example 5

[0116] The reaction process and conditions were the same as those in Example 1, except that when the reaction time was changed to 5 hours, the yield of the product in Example 1 was 48% (the reaction was incomplete due to the short reaction time).

[0117] Comparative Example 6

[0118] The reaction process and conditions were the same as in Example 1, except that the yield of the product in Example 1 was 42% when the reaction time was 40 hours. (Product decomposes if the reaction time is too long.) Comparative Example 7

[0119] The reaction process and conditions were the same as in Example 1, except that when the copper catalyst was replaced with copper oxide, the yield of the product in Example 1 was 6%.

[0120] Comparative Example 8

[0121] The reaction process and conditions were the same as those in Example 1, except that when the alcohol was replaced with methanol hexafluoroisopropanol, the yield of the product in Example 1 was 19%.

[0122] Example 11

[0123] The reaction process and conditions were the same as in Example 1, except that when olefin 1 was 1f, the reaction time was 20 hours and the yield of product 4f was 57%.

[0124] Example 12

[0125] The reaction process and conditions were the same as in Example 1, except that when olefin 1 was 1j, the reaction temperature was 100°C and the yield of product 4f was 48%.

Claims

1. A method for preparing β-boron-substituted aldehyde derivatives, characterized in that: Using the alkene 1, diboron compound 2, and carbon monoxide 3 shown in the following formula as raw materials, a β-boron-substituted aldehyde derivative 4 is generated, and the reaction formula is as follows: ， The structure of olefin 1 is Or one of 1-methylene-1,2,3,4-tetrahydronaphthalene, 1-methyleneindane, and 2-isopropylphenylnaphthalene, wherein R 1 It is one of phenyl or substituted phenyl, wherein the substituents on the benzene ring of the substituted phenyl are selected from one to five of methyl, tert-butyl, methoxy, isopropyl, n-propyl, phenoxy, and fluorine, and the number of substituents is 1 to 5; R 2 It is one of C1-C5 alkyl chains, cyclohexyl, and cyclopentyl. The catalyst is cuprous chloride, the base is potassium tert-butoxide, the solvent is tetrahydrofuran, and the ligand is 2-methylene-1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-imidazole.

2. The method for preparing β-boron-substituted aldehyde derivatives according to claim 1, characterized in that: R in olefin 1 structure 1 It is one of phenyl or substituted phenyl, wherein the substituents on the benzene ring of the substituted phenyl are selected from 1-2 of methyl, tert-butyl, methoxy, isopropyl, n-propyl, phenoxy, and fluorine, and the number of substituents is 1-2. The C1-C5 alkyl chain is one of methyl, ethyl, isobutyl, or n-butyl.

3. The method for preparing β-boron-substituted aldehyde derivatives according to claim 1 or 2, characterized in that: The specific steps are as follows: The reaction was carried out in a reactor. First, a catalyst, ligand, alcohol, base, olefin 1, diboron compound 2 and solvent were added. Then, the atmosphere in the reactor was replaced with carbon monoxide gas 3. After replacement, 5-50 bar of carbon monoxide gas was introduced and the reaction was carried out at 50-120°C for 8-36 hours. After the reaction was completed, β-boron-substituted aldehyde compound 4 was obtained by separation.

4. The method for preparing β-boron-substituted aldehyde derivatives according to claim 3, characterized in that: The specific steps are as follows: The reaction was carried out in a reactor. First, a catalyst, ligand, alcohol, base, olefin 1, diboron compound 2 and solvent were added. Then, the atmosphere in the reactor was replaced with carbon monoxide gas 3. After replacement, 5-10 bar of carbon monoxide gas was introduced and the reaction was carried out at 70-100°C for 20-24 hours. After the reaction was completed, β-boron-substituted aldehyde compound 4 was obtained by separation.

5. The method according to claim 3, characterized in that: The amount of catalyst used is 1-10 mol of the amount of olefin 1.

6. The method according to claim 5, characterized in that: The amount of catalyst used is 5-10 mol of the amount of olefin 1.

7. The method according to claim 3, characterized in that: The amount of ligand used is 1-10 mol of the amount of olefin 1.

8. The method according to claim 7, characterized in that: The amount of ligand used is 5-10 mol of the amount of olefin 1.

9. The method according to claim 3, characterized in that: The amount of base used is 100-400 mol of the amount of olefin 1.

10. The method according to claim 3, characterized in that: The amount of base used is 150-300 mol of the amount of olefin 1.

11. The method according to claim 3, characterized in that: The alcohol is one or more of tert-butanol, methanol, ethanol, and butanol, and the amount of alcohol used is 100-400 mol of the amount of olefin 1.

12. The method according to claim 11, characterized in that: The alcohol is p-tert-butanol; the amount of alcohol used is 150-250 mol of the amount of olefin 1.

13. The method according to claim 3, characterized in that: The amount of solvent used is 1.0-10.0 mL per millimole of olefin.

14. The method according to claim 13, characterized in that: The amount of solvent used is 5.0-8.0 mL per millimole of olefin.

15. The method according to claim 3, characterized in that: The amount of diboron compound 2 is 100-400 mol of the amount of aryl iodine.

16. The method according to claim 15, characterized in that: The amount of diboron compound 2 is 150-250 mol of the amount of aryl iodine.

17. The method according to claim 3, characterized in that: Before the atmosphere is replaced in the reactor, the total amount of catalyst, ligand, alcohol, base, olefin 1, diboron compound 2 and solvent in the reactor is less than 50% of the reactor volume.

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