Method for synthesizing aromatic borate through selective boronation of aromatic compounds

Abstract

The invention discloses a method for synthesizing aromatic borate through selective boronation of an aromatic compound, which comprises the following steps: (1) adding a boron reagent A into an organic solvent, and reacting under the action of organic strong alkali to obtain an active boron species and carbon negative ion intermediate reaction liquid; and (2) adding an aromatic compound Ar-X into the reaction liquid in the step (1), and carrying out boronation reaction to obtain the aromatic borate product. The method disclosed by the invention is mild in condition, simple to operate, free of transition metal participation and wide in substrate application range, and has wide research value and industrial application prospect.

Description

Technical Field

[0001] The invention relates to a method for synthesizing a compound, in particular to a method for synthesizing aromatic borate esters by selective boronization of an aromatic hydrocarbon compound. Background Art

[0002] Due to the metalloid property of boron, organic borate esters not only inherit the high stability of traditional organic compounds, but also can effectively transfer organic groups to metal centers through transmetallation reactions under the catalysis of transition metals, thereby achieving a variety of chemical transformations. At present, aromatic borate ester compounds have become a class of extremely valuable chemical raw materials, playing a wide and important role in scientific research and industrial production. Therefore, the process of introducing borate ester groups into organic compounds has always been a key topic in the field of organic chemistry. Traditional methods for preparing aromatic borate esters include: (1) first preparing the corresponding organometallic compound (Grizzg reagent, organolithium reagent, etc.) from aromatic halides, and then reacting with borate esters; (2) using palladium catalysis to couple aromatic halides with diborates. These methods have obvious disadvantages, such as requiring extreme reaction conditions (low temperature, etc.), involving dangerous active metals or expensive transition metal catalysts, easily generating transition metal residues, and requiring expensive aromatic halides as starting materials. Summary of the invention

[0003] Objective of the invention: The first objective of the present invention is to provide a method for synthesizing aromatic borate esters by selective boration of aromatic compounds under mild reaction conditions and without the need for transition metals.

[0004] Technical solution: The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds according to the present invention comprises the following steps:

[0005] (1) adding a boron reagent A to an organic solvent to react under the action of an organic strong base to obtain an active boron species and a carbon anion intermediate reaction solution;

[0006] (2) adding an aromatic compound Ar-X to the reaction solution of step (1) to carry out a borylation reaction to obtain an aromatic borate ester product; the borylation reaction temperature is 60 to 100° C.;

[0007] The synthetic route is as follows:

[0008]

[0009] Among them, R 1 is a benzene ring, a C1-C5 alkenyl group or a borate group, R 2 is C1-C5 alkyl or H; R 3 is C1-C5 alkyl or H; X is H or halogen.

[0010] In the step (1), the colorless and transparent solution rapidly changes into a dark red transparent or translucent solution during the reaction. During the reaction, the carbon anion intermediate generated in situ by the boron reagent and the organic strong base has the characteristics of a super base, and can undergo a deprotonation reaction with a series of aromatic hydrocarbons or heterocyclic aromatic hydrocarbons, and be captured by the boron species in the system to obtain the corresponding boronated product; it can also undergo a dehalogenation reaction with a series of halogenated aromatic hydrocarbons, and be captured by the boron species in the system to obtain the corresponding boronated product.

[0011] In the step (2), the reaction liquid changes from dark red to brown, light yellow or completely fades during the reaction.

[0012] Preferably, R 1 is a benzene ring, a C1-C5 alkenyl group or a borate group, R 2 is C1-C5 alkyl or H, said R 2 Methyl or H, R 3 Methyl or H.

[0013] Preferably, the R 1 is a benzene ring, R 2 Methyl or H, R 3 Methyl or H.

[0014] Preferably, the R 1 is C1-C5 alkenyl, R 2 Methyl or H, R 3 Methyl or H.

[0015] Preferably, the R 1 is a borate ester group, R 2 Methyl or H, R 3 Methyl or H.

[0016] Preferably, the boron reagent A is: 4,4,5,5-tetramethyl-2-(2-phenylpropan-2-yl)-1,3,2-dioxaborolane, 4,4,5,5-tetramethyl-2-(1-phenylethyl)-1,3,2-dioxaborolane, 2-benzyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)methane, and the structural formula is as follows:

[0017]

[0018] Among them, when R 1 is a benzene ring, R 2When it is methyl, the preparation method of the boron reagent is: in an organic solvent, α-aryl olefin and HBpin are reacted at 40-80° C. under the catalysis of nickel catalyst and strong base to generate benzyl borate. The synthesis route is as follows:

[0019]

[0020] Preferably, the borylation reaction temperature is 60-100° C., and the reaction time is 1-5 hours.

[0021] Preferably, the boronization reaction temperature is 80-100°C and the reaction time is 2.5-5 hours.

[0022] Preferably, the molar ratio of the boron reagent: the organic strong base: the aromatic compound is 1 to 3:1 to 3:1.

[0023] Preferably, the organic solvent is selected from one or more of tetrahydrofuran, 1,4-dioxane, cyclohexane and toluene.

[0024] Preferably, the aromatic compound Ar-X is selected from N-methylindole, N-ethylindole, N-phenylindole, 1,3-dimethylindole, 1,4-dimethylindole, 1,5-dimethylindole, 1,6-dimethylindole, 1,7-dimethylindole, 5-methoxy-1-methyl-1H-indole, 5-fluoro-1-methyl-1H-indole, 5-chloro-1-methyl-1H-indole, 1-methyl-5-trifluoromethyl-1H-indole, 1-methyl-7-azaindole, dibenzothiophene, dibenzofuran, N-methylpyrrole, diphenyl ether , 1,4-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, 1-fluoro-4-methoxybenzene, benzothiophene, 5-bromobenzothiophene, benzofuran, 2-n-pentylthiophene, 2-n-pentylfuran, 2-(2-thiophene)pyridine, dithiophene, 3,4-ethylenedioxythiophene, 1-bromonaphthalene, 2-bromo-1,3,5-trimethylbenzene, 4-bromo-N,N-dimethylaniline, 4-bromoanisole, 4-bromotrifluorotoluene, N,N-diethyl-4-bromobenzamide, 7-bromobenzofuran, 2-bromodibenzothiophene or 2-bromodibenzofuran. The structural formula of the above aromatic compounds is:

[0025]

[0026] Preferably, in step (2), the borylation reaction also includes post-treatment after completion, wherein the post-treatment is: adding saturated aqueous ammonium chloride solution and saturated brine to the reaction solution for quenching, then extracting with ether or ethyl acetate, separating the liquids, drying, filtering, and concentrating under reduced pressure to obtain a crude product, and the crude product is purified by chromatography to obtain an aromatic borate ester product.

[0027] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) The method has mild conditions, simple operation, no need for transition metal participation, a wide range of substrate applicability, and has broad research value and industrial application prospects; (2) The method can be used to borylate inexpensive aromatic hydrocarbon substrates, which can reduce costs; (3) The method can be used to synthesize different types of compounds by tandem oxidation reactions, coupling reactions, etc., and has the advantages of simplicity and high efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The present invention is a synthetic route diagram of the method for synthesizing aromatic borate esters by selective boronization of aromatic hydrocarbon compounds;

[0029] Figure 2 The NMR of the key carbon negative intermediate (III) and the accompanying boron-containing byproduct (IV) in Example 3 is 11 B spectroscopy and NMR 1 H spectrum;

[0030] Figure 3 For the nuclear magnetic resonance of the product in Example 3 1 H spectrum;

[0031] Figure 4 For the nuclear magnetic resonance of the product in Example 3 13 C spectrum;

[0032] Figure 5 For the nuclear magnetic resonance of the product in Example 3 11 B spectrum. DETAILED DESCRIPTION

[0033] The technical solution of the present invention is further described below in conjunction with embodiments.

[0034] Example 1

[0035] The boron reagent in the method for selectively boronizing an aromatic hydrocarbon compound to synthesize an aromatic boric ester of the present invention has a chemical name of 4,4,5,5-tetramethyl-2-(2-phenylpropan-2-yl)-1,3,2-dioxaborolane, and has the following structural formula:

[0036]

[0037] The synthetic route is as follows:

[0038]

[0039] Preparation method: In an argon-filled glove box, 128.5 mg (0.5 mmol) of nickel acetylacetonate, 760 mg (5 mmol) of cesium fluoride, 10 mL of tetrahydrofuran and 5.90 g (50 mmol) of α-methylstyrene were added to a 100 mL round-bottom flask equipped with a magnetic rod and dried in an oven overnight, and then 6.72 g (52.5 mmol) of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added to the mixture. After the reaction mixture was stirred at 40 ° C for 48 hours, 10 mL of ethyl acetate was added and exposed to air to terminate the reaction. The reaction solution was filtered through a short column filled with diatomaceous earth and silica gel and eluted with ethyl acetate. The eluate was concentrated under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography to obtain 6.37 g of a colorless oily liquid with a yield of 51% and a regioselectivity ratio of 90:10 (branched / linear). The regioselectivity ratio of the borylation product is determined by the purified mixture. 1 Determined by HNMR analysis.

[0040] The product characterization data are as follows:

[0041] 1 H NMR (400 MHz, CDCl 3 )δ7.37-7.28(m,4H),7.19-7.13(m,1H),1.38(s,6H),1.23(s,12H)ppm.

[0042] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ148.8,128.2,126.4,125.1,83.5,25.7,24.6ppm.

[0043] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ34.2ppm.

[0044] Example 2

[0045] The boron reagent in the method for selectively boronizing an aromatic hydrocarbon compound to synthesize an aromatic boric acid ester of the present invention has a chemical name of 4,4,5,5-tetramethyl-2-(1-phenylethyl)-1,3,2-dioxaborolane, and has the following structural formula:

[0046]

[0047] The synthetic route is as follows:

[0048]

[0049] Preparation method: In an argon-filled glove box, 2.6 mg (0.01 mmol) of nickel acetylacetonate, 152 mg (1.0 mmol) of cesium fluoride, 10 mL of tetrahydrofuran and 2.36 g (20 mmol) of styrene were added to a 100 mL round-bottom flask equipped with a magnet and dried overnight in an oven, and then 2.69 g (21 mmol) of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added to the mixture. After the reaction mixture was stirred at 80 ° C for 18 hours, 10 mL of ethyl acetate was added and exposed to air to terminate the reaction. The reaction solution was filtered through a short column filled with diatomaceous earth and silica gel and eluted with ethyl acetate. The eluate was concentrated under reduced pressure to obtain a crude product, which was purified by silica gel column chromatography to obtain 3.50 g of a colorless oily liquid with a yield of 75%.

[0050] The product characterization data are as follows:

[0051] 1 H NMR (400 MHz, CDCl 3 )δ7.33-7.25(m,4H),7.20-7.15(m,1H),2.49(q,J=7.5Hz,1H),1.38(d,J=7.5Hz,3H),1.26(s,6H),1.25(s,6H)ppm.

[0052] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ145.1,128.4,127.9,125.2,83.4,24.76,24.72,17.2ppm.

[0053] Other boron reagents 2-benzyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)methane are all commercially available reagents with the following structural formulas:

[0054]

[0055] Example 3

[0056] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention is used to synthesize 1-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-1H-indole, the structural formula of which is as follows:

[0057]

[0058] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 26.2 mg (0.2 mmol) of N-methylindole to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 37.8 mg of a white solid with a yield of 74%.

[0059] Depend on Figure 2 It can be obtained that the corresponding chemical shift of the carbon negative intermediate is in good agreement with the NMR data calculated by DFT, confirming that a highly active carbon negative intermediate is produced in the first step of the reaction.

[0060] The product characterization data are as follows:

[0061] 1 H NMR (400 MHz, CDCl 3 )δ7.65(d,J=8.0Hz,1H),7.36(d,J=8.3Hz,1H),7.29-7.25(m,1H),7.15(s,1H),7.09(t,J=7.9Hz,1H),3.98(s,3H),1.38(s,12H)ppm.

[0062] 13 C{ 1 H}NMR (101 MHz, CDCl 3 ): δ140.3,128.0,123.3,121.7,119.4,114.4,109.8,83.8,32.4,25.0ppm.

[0063] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ28.9ppm.

[0064] Example 4

[0065] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention is used to synthesize 1-ethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-1H-indole, the structural formula of which is as follows:

[0066]

[0067] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 29.0 mg (0.2 mmol) of N-ethylindole to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 35.2 mg of light yellow oily liquid with a yield of 65%.

[0068] The product characterization data are as follows:

[0069] 1 H NMR (400 MHz, CDCl 3 )δ7.65(d,J=8.0Hz,1H),7.37(d,J=8.3Hz,1H),7.27-7.23(m,1H),7.14(s,1H),7.08(t,J=7.9Hz,1H),4.48(q,J=7.1Hz,2H),1.37(m,15H)ppm.

[0070] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ139.1,128.2,123.2,121.9,119.3,114.7,109.8,83.8,40.6,25.0,16.2ppm.

[0071] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ29.1ppm.

[0072] HRMS(ESI):calculated for C 16 H 23 BNO 2 + [M+H] + 272.1816; found 272.1810.

[0073] Example 5

[0074] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention is used to synthesize 1-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-1H-indole, the structural formula of which is as follows:

[0075]

[0076] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 38.7 mg (0.2 mmol) of N-phenylindole to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 52.8 mg of yellow-green oily liquid with a yield of 83%.

[0077] The product characterization data are as follows:

[0078] 1 H NMR (400 MHz, CDCl 3 )δ7.68(d,J=7.8Hz,1H),7.48-7.41(m,2H),7.39-7.37(m,3H),7.28(d,J=8.3Hz, 1H),7.26(s,1H),7.19(t,J=7.0Hz,1H),7.11(t,J=6.8Hz,1H),1.20(s,12H)ppm.

[0079] 13 C{ 1 H}NMR (101 MHz, CDCl 3)δ140.6,139.9,128.7,128.4,127.8,127.2,123.8,121.6,120.2,115.9,111.0,83.8,24.7ppm.

[0080] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ28.9ppm.

[0081] Example 6

[0082] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention synthesizes 1,3-dimethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-1H-indole, and the structural formula thereof is as follows:

[0083]

[0084] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 29.0 mg (0.2 mmol) of 1,3-dimethylindole to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 28.7 mg of a white solid with a yield of 53%.

[0085] The product characterization data are as follows:

[0086] 1 H NMR (400 MHz, CDCl 3 )δ7.57(d,J=8.0Hz,1H),7.30-7.17(m,2H),7.05-7.01(m,1H),3.88(s,3H),2.52(s,3H),1.33(s,12H)ppm.

[0087] 13 C{ 1 H}NMR (101 MHz, CDCl 3)δ140.0,128.6,124.9,123.4,119.9,118.5,109.6,83.3,32.3,25.0,10.3ppm.

[0088] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ29.6ppm.

[0089] Example 7

[0090] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention synthesizes 1,4-dimethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole, and the structural formula thereof is as follows:

[0091]

[0092] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 29.0 mg (0.2 mmol) of 1,4-dimethylindole to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 23.3 mg of a white solid with a yield of 43%.

[0093] The product characterization data are as follows:

[0094] 1 H NMR (400 MHz, CDCl 3 )δ7.20-7.18(m,3H),6.90-6.88(m,1H),3.98(s,3H),2.57(s,3H),1.39(s,12H)ppm.

[0095] 13 C{ 1 H}NMR (101 MHz, CDCl 3)δ140.2,131.4,128.0,123.6,119.5,113.0,107.5,83.8,32.5,25.0,18.8ppm.

[0096] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ29.1ppm.

[0097] Example 8

[0098] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention is used to synthesize 1,5-dimethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-1H-indole, the structural formula of which is as follows:

[0099]

[0100] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 29.0 mg (0.2 mmol) of 1,5-dimethylindole to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 26.0 mg of a white solid with a yield of 48%.

[0101] The product characterization data are as follows:

[0102] 1 H NMR (400 MHz, CDCl 3 )δ7.42(s,1H),7.24(d,J=8.4Hz,1H),7.10(d,J=10.2Hz,1H),7.05(s,1H),3.95(s,3H),2.45(s,3H),1.38(s,12H)ppm.

[0103] 13 C{ 1 H}NMR (101 MHz, CDCl 3)δ138.9,128.5,128.3,125.2,121.1,113.8,109.5,83.8,32.4,25.0,21.5ppm.

[0104] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ29.0ppm.

[0105] Example 9

[0106] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention synthesizes 1,6-dimethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole, and the structural formula thereof is as follows:

[0107]

[0108] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 29.0 mg (0.2 mmol) of 1,6-dimethylindole to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 34.5 mg of a white solid with a yield of 64%.

[0109] The product characterization data are as follows:

[0110] 1 H NMR (400 MHz, CDCl 3 )δ7.52(d,J=8.1Hz,1H),7.14(s,1H),7.09(s,1H),6.93(d,J=8.1Hz,1H),3.94(s,3H),2.50(s,3H),1.37(s,12H)ppm.

[0111] 13 C{ 1 H}NMR (101 MHz, CDCl 3)δ140.8,133.3,125.9,121.5,121.3,114.4,109.7,83.7,32.3,25.0,22.2ppm.

[0112] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ28.9ppm.

[0113] Example 10

[0114] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention is used to synthesize 1,7-dimethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole, the structural formula of which is as follows:

[0115]

[0116] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 29.0 mg (0.2 mmol) of 1,7-dimethylindole to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 34.3 mg of a white solid with a yield of 63%.

[0117] The product characterization data are as follows:

[0118] 1 H NMR (400 MHz, CDCl 3 )δ7.49-7.42(m,1H),7.11(s,1H),6.96-6.91(m,2H),4.27(s,3H),2.80(s,3H),1.37(s,12H)ppm.

[0119] 13 C{ 1 H}NMR (101 MHz, CDCl 3)δ139.4,129.0,126.1,121.8,120.0,119.6,115.2,83.8,35.8,25.0,20.6ppm.

[0120] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ29.0ppm.

[0121] Embodiment 11

[0122] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention is used to synthesize 5-methoxy-1-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-1H-indole, and the structural formula thereof is as follows:

[0123]

[0124] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction liquid; add 32.2 mg (0.2 mmol) of 5-methoxy-1-methyl-1H-indole to the above reaction liquid, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 41.8 mg of a white solid with a yield of 73%.

[0125] The product characterization data are as follows:

[0126] 1 H NMR (400 MHz, CDCl 3 )δ7.24(d,J=9.0Hz,1H),7.07(d,J=2.4Hz,1H),7.05(s,1H),6.95(dd,J=9.0,2.5Hz,1H),3.95(s,3H),3.86(s,3H),1.37(s,12H)ppm.

[0127] 13 C{ 1H}NMR (101 MHz, CDCl 3 )δ154.1,136.0,128.2,114.5,113.6,110.6,102.3,83.8,55.9,32.5,25.0ppm.

[0128] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ29.2ppm.

[0129] Example 12

[0130] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention is used to synthesize 5-fluoro-1-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-1H-indole, the structural formula of which is as follows:

[0131]

[0132] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 29.8 mg (0.2 mmol) of 5-fluoro-1-methyl-1H-indole to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 50:1) to obtain 17.4 mg of a white solid with a yield of 32%.

[0133] The product characterization data are as follows:

[0134] 1 H NMR (400 MHz, CDCl 3 )δ7.27-7.22(m,2H),7.06(s,1H),7.03-6.98(m,1H),3.95(s,3H),1.36(s,12H)ppm.

[0135] 13 C{ 1 H}NMR (101 MHz, CDCl 3)δ157.9(d,J=234.4Hz),137.1,128.0(d,J=9.6Hz),113.9(d,J=5.2Hz),112.0 (d, J=26.8Hz), 110.4 (d, J=9.6Hz), 105.8 (d, J=22.9Hz), 84.0, 32.6, 25.0ppm.

[0136] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ29.0ppm.

[0137] 19 F{ 1 H}NMR (376MHz, CDCl 3 )δ-125.7ppm.

[0138] Example 13

[0139] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention is used to synthesize 5-chloro-1-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-1H-indole, the structural formula of which is as follows:

[0140]

[0141] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 33.1 mg (0.2 mmol) of 5-chloro-1-methyl-1H-indole to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 44.4 mg of a white solid with a yield of 76%.

[0142] The product characterization data are as follows:

[0143] 1 H NMR (400 MHz, CDCl 3)δ7.60(d,J=1.9Hz,1H),7.25(d,J=8.4Hz,1H),7.20(dd,J=8.8,2.0Hz,1H),7.05(s,1H),3.95(s,3H),1.37(s,12H)ppm.

[0144] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ138.7,128.9,125.2,123.6,120.8,113.7,110.8,84.0,32.6,25.0ppm.

[0145] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ28.8ppm.

[0146] Embodiment 14

[0147] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention is used to synthesize 1-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(trifluoromethyl)-1H-indole, the structural formula of which is as follows:

[0148]

[0149] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 39.8 mg (0.2 mmol) of 1-methyl-5-(trifluoromethyl)-1H-indole to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 50:1) to obtain 26.6 mg of a yellow solid with a yield of 41%.

[0150] The product characterization data are as follows:

[0151] 1 H NMR (400 MHz, CDCl3 )δ7.94(s,1H),7.47(d,J=8.8Hz,1H),7.40(d,J=8.7Hz,1H),7.20(s,1H),4.00(s,3H),1.38(s,12H)ppm.

[0152] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ141.3,127.2,125.6(q,J=271.4Hz),121.8(q,J=31.8Hz),119.8(q,J=3.6Hz),119.5(q,J=4.2Hz),115.2,110.1,84.2,32.6,25.0ppm.

[0153] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ28.8ppm.

[0154] 19 F{ 1 H}NMR (376MHz, CDCl 3 )δ-60.3(s,3F)ppm.

[0155] Embodiment 15

[0156] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention synthesizes 1-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-1H-pyrrolo[2,3-b]pyridine, and the structural formula thereof is as follows:

[0157]

[0158] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 26.4 mg (0.2 mmol) of 1-methyl-7-azaindole to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F254 , mobile phase petroleum ether: ethyl acetate = 20:1) to obtain 33.1 mg of a white solid with a yield of 64%.

[0159] The product characterization data are as follows:

[0160] 1 H NMR (400 MHz, CDCl 3 )δ8.40(d,J=4.6,1H),7.92(d,J=7.8,1H),7.07(s,1H),7.03(dd,J=7.8,4.6Hz,1H),4.07(s,3H),1.37(s,12H)ppm.

[0161] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ150.5,144.9,129.7,120.2,115.7,112.2,84.1,31.0,25.0ppm.

[0162] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ28.8ppm.

[0163] Example 16

[0164] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention synthesizes 2-(dibenzo[b,d]thiophene-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and the structural formula thereof is as follows:

[0165]

[0166] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 36.8 mg (0.2 mmol) of dibenzothiophene to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254, mobile phase petroleum ether: ethyl acetate = 50:1) to obtain 55.2 mg of light yellow oily liquid with a yield of 89%.

[0167] The product characterization data are as follows:

[0168] 1 H NMR (400 MHz, CDCl 3 )δ8.27(dd,J=7.8,1.3Hz,1H),8.19-8.14(m,1H),7.96(dd,J=7.1,1.3Hz,1H),7.91-7.87(m,1H),7.53-7.42(m,3H),1.45(s,12H)ppm.

[0169] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ146.3,140.6,135.3,135.2,134.4,126.7,124.4,124.2,123.8,122.7,121.4,84.5,25.1ppm.

[0170] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ31.2ppm.

[0171] Embodiment 17

[0172] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention synthesizes 2-(dibenzo[b,d]furan-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and the structural formula thereof is as follows:

[0173]

[0174] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 36.8 mg (0.2 mmol) of dibenzofuran to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 50:1) to obtain 35.8 mg of a white solid with a yield of 61%.

[0175] The product characterization data are as follows:

[0176] 1 H NMR (400 MHz, CDCl 3 )δ8.06(d,J=7.6,1H),7.94(d,J=7.7,1H),7.90(d,J=7.3,1H),7.68(d,J=8.3,1H),7.45(t,J=8.5,1H),7.39-7.30(m,2H),1.45(s,12H)ppm.

[0177] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ160.6,156.5,134.5,127.1,124.1,123.8,122.6,122.4,120.5,112.5,84.2,25.1ppm.

[0178] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ31.0ppm.

[0179] Embodiment 18

[0180] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention synthesizes 4,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)dibenzofuran, the structural formula of which is as follows:

[0181]

[0182] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 36.8 mg (0.2 mmol) of dibenzofuran to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 50:1) to obtain 24.1 mg of a white solid with a yield of 29%.

[0183] The product characterization data are as follows:

[0184] 1 H NMR (400 MHz, CDCl 3 )δ8.02(d,J=7.6Hz,2H),7.84(d,J=7.3Hz,2H),7.32(t,J=7.5Hz,2H),1.46(s,24H)ppm.

[0185] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ160.9,134.0,123.6,123.5,122.2,84.0,25.3ppm.

[0186] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ31.1ppm.

[0187] HRMS(ESI):calculated for C 24 H 31 B 2 O 5 + [M+H] + 421.2352; found 421.2347.

[0188] Embodiment 19

[0189] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention synthesizes 1-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrole, and the structural formula thereof is as follows:

[0190]

[0191] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction liquid; add 16.2 mg (0.2 mmol) of N-methylpyrrole to the above reaction liquid, seal it and move out of the glove box, and stir at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, and the product NMR yield is 51% (with dibenzyl ether as an internal standard).

[0192] 2-Bromopyridine was used as a coupling reagent and connected in series with the Suzuki-Miyaura coupling reaction: After the borylation process was completed, 2.3 mg (0.01 mmol) of palladium acetate, 11.1 mg (0.02 mmol) of 1,1'-bis(diphenylphosphino)ferrocene (DPPF), 29.7 mg (0.3 mmol) of cuprous chloride, 47.4 mg (0.3 mmol) of 2-bromopyridine and anhydrous dimethylformamide (1.0 mL) were directly added to the reaction mixture in an argon-filled glove box. The reaction tube was sealed and taken out of the glove box and stirred at 100 ° C for 16 hours. After the reaction was completed, 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine were added to the reaction vessel to quench, and then extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which was subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 23.3 mg of green oily liquid with a yield of 74%. The reaction route involved is as follows:

[0193]

[0194] The product characterization data are as follows:

[0195]

[0196] 1 H NMR (400 MHz, CDCl 3)δ8.57(ddd,J=4.9,1.9,1.0Hz,1H),7.64(td,J=7.7,1.9Hz,1H),7.53(dt,J=8.0,1.1Hz,1H),7.07(ddd,J=7.4, 4.9,1.2Hz,1H),6.74(t,J=2.2Hz,1H),6.58(dd,J=3.8,1.8Hz,1H),6.19(dd,J=3.7,2.6Hz,1H),4.00(s,3H)ppm.

[0197] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ152.9,148.7,136.3,132.5,126.5,121.6,120.4,110.8,107.8,37.0ppm.

[0198] Embodiment 20

[0199] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention is used to synthesize 1-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-1H-indole, the structural formula of which is as follows:

[0200]

[0201] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction liquid; add 34.0 mg (0.2 mmol) of diphenyl ether to the above reaction liquid, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 50: 1) to obtain 16.8 mg of yellow oily liquid with a yield of 28% (NMR yield of 44%).

[0202] The product characterization data are as follows:

[0203] 1 H NMR (400 MHz, CDCl 3)δ7.76(d,J=7.4,1H),7.43(dd,J=8.1,7.4Hz,1H),7.26-7.20(m,2H),7.1 7(t,J=7.4Hz,1H),7.03-6.94(m,2H),6.89-6.84(m,2H),1.15(s,12H)ppm.

[0204] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ160.6,159.8,136.8,132.89,129.5,124.1,121.8,121.0,117.2,83.8,24.7ppm.

[0205] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ30.6ppm.

[0206] HRMS(ESI):calculated for C 18 H 22 BO 3 + [M+H] + 297.1657; found 297.1949.

[0207] In series with the oxidation reaction, the corresponding hydroxyl compound was prepared: in a glove box filled with argon, 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran were added to a 10 mL Schlenk tube, and stirred at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; 34.0 mg (0.2 mmol) of diphenyl ether was added to the above reaction solution, and the glove box was removed after sealing, and stirred at 80°C for 2.5 hours; after the reaction was completed, the reaction mixture was cooled to room temperature, and then 92.6 mg (0.6 mmol) of sodium perborate tetrahydrate and 1 mL of water were added. The mixture was stirred at room temperature for another 3 hours. Then, 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine were added to the reaction mixture, and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 18.2 mg of white solid with a yield of 49%. The reaction route involved is as follows:

[0208]

[0209] The product characterization data are as follows:

[0210] 1 H NMR (400 MHz, CDCl 3 )δ7.39-7.31(m,2H),7.16-7.10(m,1H),7.07-7.00(m,4H),6.92-6.82(m,2H),5.63(s,1H)ppm.

[0211] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ156.9,147.7,143.6,130.0,124.9,123.7,120.8,119.1,118.1,116.3ppm.

[0212] Embodiment 21

[0213] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention synthesizes 2,2'-(oxybis(2,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane), the structural formula of which is as follows:

[0214]

[0215] Preparation method: In a glove box filled with argon, add 336.6 mg (3.0 mmol) of potassium tert-butoxide, 738.5 mg (3.0 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 5 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20 ° C) for 10 min to obtain an activated carbon negative intermediate reaction liquid; add 170.0 mg (1.0 mmol) of diphenyl ether to the above reaction liquid, seal it and move out of the glove box, and stir at 80 ° C for 4 hours; after the reaction is completed, add 15 mL of saturated ammonium chloride solution and 5 mL of saturated brine to the reaction container to quench, and extract with ethyl acetate (3×10 mL). The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a light yellow gel-like crude product, which is purified by recrystallization from hexane to obtain 226.6 mg of a white solid with a yield of 54%.

[0216] The product characterization data are as follows:

[0217] mp126.5-128.5℃.

[0218] 1 H NMR (400 MHz, CDCl3 )δ7.72(dd,J=7.3,1.9Hz,2H),7.32(ddd,J=8.2,7.3,1.9Hz,2H),7.04(td,J=7.3,1.0Hz,2H),6.75(dd,J=8.3,1.0Hz,2H),1.21(s,24H)ppm.

[0219] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ162.9,136.7,132.3,122.4,118.3,83.5,24.8ppm.

[0220] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ30.8ppm.

[0221] HRMS(ESI):calculated for C 24 H 33 B 2 O 5 + [M+H] + 423.2509; found 423.2497.

[0222] In series with the oxidation reaction, the corresponding hydroxyl compound was prepared: in a glove box filled with argon, 67.3 mg (0.6 mmol) of potassium tert-butoxide, 147.6 mg (0.6 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran were added to a 10 mL Schlenk tube, and stirred at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; 34.0 mg (0.2 mmol) of diphenyl ether was added to the above reaction solution, and the glove box was removed after sealing, and stirred at 80°C for 2.5 hours; after the reaction was completed, the reaction mixture was cooled to room temperature, and then 92.6 mg (0.6 mmol) of sodium perborate tetrahydrate and 1 mL of water were added. The mixture was stirred at room temperature for another 3 hours. Then, 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine were added to the reaction mixture, and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: isopropanol = 20:1) to obtain 29.0 mg of a white solid with a yield of 72%. The reaction route involved is as follows:

[0223]

[0224] The product characterization data are as follows:

[0225] mp124-126℃.

[0226] 1 H NMR (400 MHz, CDCl 3 )δ7.08-7.02(m,4H),6.89-6.81(m,4H),5.78(s,2H)ppm.

[0227] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ147.2,143.6,125.2,121.0,118.3,116.7ppm.

[0228] HRMS(ESI):calculated for C 12 H 9 O 3 - [MH] – 201.0557; found 201.0550.

[0229] Embodiment 22

[0230] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention synthesizes 2-(2,5-dimethoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and the structural formula thereof is as follows:

[0231]

[0232] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction liquid; add 27.6 mg (0.2 mmol) of 1,4-dimethoxybenzene to the above reaction liquid, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is purified by rapid column chromatography (solid phase silica gel 60F 254, mobile phase petroleum ether: ethyl acetate = 50:1 to 20:1) to obtain 34.5 mg of a colorless solid with a yield of 65% (NMR yield was 96%, with dibenzyl ether as the internal standard).

[0233] The product characterization data are as follows:

[0234] 1 H NMR (400 MHz, CDCl 3 )δ7.21(d,J=3.2Hz,1H),6.93(dd,J=8.9,3.2Hz,1H),6.80(d,J=8.9Hz,1H),3.79(s,3H),3.78(s,3H),1.35(s,12H)ppm.

[0235] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ158.7,153.4,121.2,118.2,112.4,83.7,56.9,56.0,25.0ppm.

[0236] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ31.0ppm.

[0237] In series with the oxidation reaction, the corresponding hydroxyl compound was prepared: in a glove box filled with argon, 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran were added to a 10 mL Schlenk tube, and stirred at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; 27.6 mg (0.2 mmol) of 1,4-dimethoxybenzene was added to the above reaction solution, and the glove box was removed after sealing, and stirred at 80°C for 2.5 hours; after the reaction was completed, the reaction mixture was cooled to room temperature, and then 92.6 mg (0.6 mmol) of sodium perborate tetrahydrate and 1 mL of water were added. The mixture was stirred at room temperature for another 3 hours. Then, 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine were added to the reaction mixture, and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) was purified to obtain 18.4 mg of a light yellow oily liquid with a yield of 60%. The reaction route involved is as follows:

[0238]

[0239] The product characterization data are as follows:

[0240]

[0241] 1 H NMR (400 MHz, CDCl 3 )δ6.77(d,J=8.8Hz,1H),6.56(d,J=2.9Hz,1H),6.38(dd,J=8.8,2.9Hz,1H),5.69(s,1H),3.84(s,3H),3.75(s,3H)ppm.

[0242] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ154.7,146.6,141.1,111.6,104.4,101.9,56.7,55.8ppm.

[0243] Embodiment 23

[0244] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention synthesizes 2-(2,6-dimethoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and the structural formula thereof is as follows:

[0245]

[0246] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction liquid; add 27.6 mg (0.2 mmol) of 1,3-dimethoxybenzene to the above reaction liquid, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative rapid column chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 10: 1 to 5: 1) to obtain 8.5 mg of a colorless solid with a yield of 16%.

[0247] The product characterization data are as follows:

[0248] 1H NMR (400 MHz, CDCl 3 )δ7.23(t,J=8.3Hz,1H),6.46(d,J=8.3Hz,2H),3.76(s,6H),1.38(s,12H)ppm.

[0249] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ163.6,131.5,103.4,83.9,55.8,24.8ppm.

[0250] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ32.0ppm.

[0251] HRMS(ESI):calculated for C 14 H 22 BO 4 + [M+H] + 265.1606; found 265.1599.

[0252] In series with the oxidation reaction, the corresponding hydroxyl compound was prepared: in a glove box filled with argon, 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran were added to a 10 mL Schlenk tube, and stirred at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; 27.6 mg (0.2 mmol) of 1,3-dimethoxybenzene was added to the above reaction solution, and the glove box was removed after sealing, and stirred at 80°C for 2.5 hours; after the reaction was completed, the reaction mixture was cooled to room temperature, and then 92.6 mg (0.6 mmol) of sodium perborate tetrahydrate and 1 mL of water were added. The mixture was stirred at room temperature for another 3 hours. Then, 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine were added to the reaction mixture, and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 15.1 mg of yellow oily liquid with a yield of 49%. The reaction route involved is as follows:

[0253]

[0254] The product characterization data are as follows:

[0255] 1 H NMR (400 MHz, CDCl 3 )δ6.80(dd,J=8.7,7.9Hz,1H),6.58(d,J=8.3Hz,2H),5.53(s,1H),3.89(s,6H)ppm.

[0256] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ147.4,135.0,119.2,105.1,56.4ppm.

[0257] Embodiment 24

[0258] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention is used to synthesize 1-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-1H-indole, the structural formula of which is as follows:

[0259]

[0260] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction liquid; add 21.6 mg (0.2 mmol) of anisole to the above reaction liquid, seal it and move out of the glove box, and stir at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, and the product NMR yield is 58% (with dibenzyl ether as an internal standard).

[0261] In series with the oxidation reaction, the corresponding hydroxyl compound was prepared: in a glove box filled with argon, 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran were added to a 10 mL Schlenk tube, and stirred at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; 21.6 mg (0.2 mmol) of anisole was added to the above reaction solution, and the glove box was removed after sealing, and stirred at 80°C for 2.5 hours; after the reaction was completed, the reaction mixture was cooled to room temperature, and then 92.6 mg (0.6 mmol) of sodium perborate tetrahydrate and 1 mL of water were added. The mixture was stirred at room temperature for another 3 hours. Then, 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine were added to the reaction mixture, and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) was purified to obtain 10.8 mg of yellow oily liquid with a yield of 44%. The reaction route involved is as follows:

[0262]

[0263] The product characterization data are as follows:

[0264] 1 H NMR(400MHz,Chloroform-d)δ6.97-6.91(m,1H),6.90-6.84(m,3H),5.64(s,1H),3.89(s,3H)ppm.

[0265] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ146.7,145.8,121.6,120.3,114.7,110.9,56.0ppm.

[0266] Embodiment 25

[0267] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention synthesizes 2-(2-fluoro-5-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and the structural formula thereof is as follows:

[0268]

[0269] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction liquid; add 25.2 mg (0.2 mmol) of 1-fluoro-4-methoxybenzene to the above reaction liquid, seal it and move out of the glove box, and stir at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, and the product NMR yield is 74% (with dibenzyl ether as an internal standard).

[0270] In series with the oxidation reaction, the corresponding hydroxyl compound was prepared: in a glove box filled with argon, 33.7 mg (0.3 mmol) of potassium tert-butoxide, 73.8 mg (0.3 mmol) of 4,4,5,5-tetramethyl-2-(2-phenylpropane-2-yl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran were added to a 10 mL Schlenk tube, and stirred at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; 25.2 mg (0.2 mmol) of 1-fluoro-4-methoxybenzene was added to the above reaction solution, and the glove box was removed after sealing, and stirred at 80°C for 2.5 hours; after the reaction was completed, the reaction mixture was cooled to room temperature, and then 92.6 mg (0.6 mmol) of sodium perborate tetrahydrate and 1 mL of water were added. The mixture was stirred at room temperature for another 3 hours. Then, 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine were added to the reaction mixture, and extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) was purified to obtain 18.8 mg of yellow oily liquid with a yield of 66%. The reaction route involved is as follows:

[0271]

[0272] The product characterization data are as follows:

[0273]

[0274] 1 H NMR (400 MHz, CDCl 3)δ6.97(dd,J=10.2,9.0Hz,1H),6.57(dd,J=7.3,3.0Hz,1H),6.37(ddd,J=9.0,3.6,3.0Hz,1H),5.43(d,J=3.9Hz,1H),3.75(s,3H)ppm.

[0275] 13 C{ 1 H}NMR (101 MHz, CDCl 3 ) δ156.5, 146.0 (d, J = 229.3Hz), 144.2 (d, J = 15.6Hz), 115.6 (d, J = 19.8Hz), 105.6 (d, J = 6.4Hz), 103.2, 55.9ppm.

[0276] 19 F{ 1 H}NMR (376MHz, CDCl 3 )δ-151.1ppm.

[0277] Embodiment 26

[0278] The method for synthesizing aromatic borate esters by selective boronization of aromatic hydrocarbon compounds of the present invention synthesizes 2-(benzo[b]thiophene-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and the structural formula thereof is as follows:

[0279]

[0280] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 52.4 mg (0.3 mmol) of 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction liquid; add 36.8 mg (0.2 mmol) of benzothiophene to the above reaction liquid, seal it and move out of the glove box, and stir at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to directly obtain 46.6 mg of a yellow colloidal solid with a yield of 90%.

[0281] The product characterization data are as follows:

[0282] 1 H NMR (400 MHz, CDCl 3)δ7.93-7.89(m,2H),7.87-7.84(m,1H),7.40-7.33(m,2H),1.39(s,12H)ppm.

[0283] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ143.9,140.6,134.6,125.4,124.5,124.2,122.7,84.6,24.9ppm.

[0284] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ29.5ppm.

[0285] Embodiment 27

[0286] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention synthesizes 2-(5-bromobenzo[b]thiophene-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and the structural formula thereof is as follows:

[0287]

[0288] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 52.4 mg (0.3 mmol) of 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 42.6 mg (0.2 mmol) of 5-bromobenzothiophene to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 50:1) to obtain 51.9 mg of a white solid with a yield of 77%.

[0289] The product characterization data are as follows:

[0290] mp64-65℃.

[0291] 1 H NMR (400 MHz, CDCl 3)δ7.98(d,J=1.8Hz,1H),7.79(s,1H),7.75(d,J=8.6,1H),7.45(dd,J=8.6,1.9Hz,1H),1.38(s,12H)ppm.

[0292] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ142.4,142.2,133.5,128.4,126.9,123.9,118.3,84.8,24.9ppm.

[0293] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ29.4ppm.

[0294] HRMS(ESI):calculated for C 14 H 17 BBr 2 S + [M+H] + 339.0220; found 339.0215.

[0295] Embodiment 28

[0296] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention synthesizes 2-(benzofuran-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and the structural formula thereof is as follows:

[0297]

[0298] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 37.0 mg (0.22 mmol) of 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction liquid; add 23.6 mg (0.2 mmol) of benzofuran to the above reaction liquid, seal it and move out of the glove box, and stir at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to directly obtain 45.0 mg of a yellow solid with a yield of 92%.

[0299] The product characterization data are as follows:

[0300] 1 H NMR (400 MHz, CDCl 3 )δ7.49(d,J=7.8Hz,1H),7.43(d,J=8.3Hz,1H),7.26(s,1H),7.20(t,J=7.7Hz,1H),7.13-7.06(m,1H),1.25(s,12H)ppm.

[0301] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ157.7,127.6,126.1,122.9,122.0,119.7,112.1,84.8,24.9ppm.

[0302] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ27.9ppm.

[0303] Embodiment 29

[0304] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention synthesizes 4,4,5,5-tetramethyl-2-(5-pentylthiophene-2-yl)-1,3,2-dioxaborolane, and the structural formula thereof is as follows:

[0305]

[0306] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 52.4 mg (0.3 mmol) of 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 30.9 mg (0.2 mmol) of 2-n-pentylthiophene to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 38.0 mg of a red-brown oily liquid with a yield of 68%.

[0307] The product characterization data are as follows:

[0308] 1H NMR (400 MHz, CDCl 3 )δ7.47(d,J=3.4Hz,1H),6.86(d,J=3.5Hz,1H),2.91-2.80(m,2H),1.74-1.64(m,2H),1.35-1.29(m,16H),0.93-0.85(m,3H)ppm.

[0309] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ153.9,137.5,126.0,84.0,31.5,31.4,30.3,24.9,22.5,14.1ppm.

[0310] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ29.2ppm.

[0311] HRMS(ESI):calculated for C 15 H 26 BO 2 S + [M+H] + 281.1741; found 281.1735.

[0312] Embodiment 30

[0313] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention synthesizes 4,4,5,5-tetramethyl-2-(5-pentylthiophene-2-yl)-1,3,2-dioxaborolane, and the structural formula thereof is as follows:

[0314]

[0315] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 37.0 mg (0.22 mmol) of 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction liquid; add 27.6 mg (0.2 mmol) of 2-n-pentylfuran to the above reaction liquid, seal it and move out of the glove box, and stir at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to directly obtain 29.4 mg of a yellow oily liquid with a yield of 56%.

[0316] The product characterization data are as follows:

[0317] 1 H NMR (400 MHz, CDCl 3 )δ7.00(d,J=3.3Hz,1H),6.04(d,J=3.3Hz,1H),2.67(t,J=7.7Hz,2H),1.71-1.60(m,2H),1.34(s,16H),0.93-0.85(m,3H)ppm.

[0318] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ162.5,124.8,106.0,84.1,31.6,28.4,27.8,24.9,22.5,14.12ppm.

[0319] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ27.1ppm.

[0320] HRMS(ESI):calculated for C 15 H 26 BO 3 + [M+H] + 265.1970; found 265.1966.

[0321] Embodiment 31

[0322] The method for synthesizing aromatic borate esters by selective boronization of aromatic hydrocarbon compounds of the present invention is used to synthesize 2-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, the structural formula of which is as follows:

[0323]

[0324] Preparation method: In a glove box filled with argon, add 67.4 mg (0.6 mmol) of potassium tert-butoxide, 100.8 mg (0.6 mmol) of 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 28.4 mg (0.2 mmol) of 3,4-ethylenedioxythiophene to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ether = 2:1) to obtain 18.8 mg of a white solid with a yield of 35%.

[0325] The product characterization data are as follows:

[0326] 1 H NMR (400 MHz, CDCl 3 )δ6.63(s,1H),4.32-4.28(m,2H),4.20-4.16(m,2H),1.34(s,12H)ppm.

[0327] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ149.2,142.5,107.6,84.0,65.2,64.4,24.9ppm.

[0328] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ28.4ppm.

[0329] Embodiment 32

[0330] The method for synthesizing aromatic borate esters by selective boronization of aromatic hydrocarbon compounds of the present invention is used to synthesize 5,5'-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2'-bithiophene, the structural formula of which is as follows:

[0331]

[0332] Preparation method: In a glove box filled with argon, add 56.2 mg (0.5 mmol) of potassium tert-butoxide, 73.9 mg (0.44 mmol) of 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction liquid; add 33.3 mg (0.2 mmol) of dithiophene to the above reaction liquid, seal it and move out of the glove box, and stir at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to directly obtain 65.6 mg of dark green solid with a yield of 78%.

[0333] The product characterization data are as follows:

[0334] 1 H NMR (400 MHz, CDCl 3 )δ7.53(d,J=3.6Hz,2H),7.29(d,J=3.6Hz,2H),1.35(s,24H)ppm.

[0335] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ144.0,138.1,125.8,84.4,24.9ppm.

[0336] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ28.6ppm.

[0337] Embodiment 33

[0338] The method for synthesizing aromatic borate esters by selective boronization of aromatic hydrocarbon compounds of the present invention is used to synthesize 2-(5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene-2-yl)pyridine, and the structural formula thereof is as follows:

[0339]

[0340] Preparation method: In a glove box filled with argon, add 33.7 mg (0.3 mmol) of potassium tert-butoxide, 52.4 mg (0.3 mmol) of 2-allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to a 10 mL Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction liquid; add 32.2 mg (0.2 mmol) of 2-(2-thiophene)pyridine to the above reaction liquid, seal it and move it out of the glove box, and stir it at 80°C for 2.5 hours; after the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine to the reaction container to quench, and extract with ether. The organic phase is dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which is subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 26.8 mg of a yellow solid with a yield of 47%.

[0341] The product characterization data are as follows:

[0342] 1 H NMR (400 MHz, CDCl 3 )δ8.59-8.57(m,1H),7.69-7.65(m,3H),7.62(d,J=3.6Hz,1H),7.15(ddd,J=6.8,4.8,2.1Hz,1H),1.35(s,12H)ppm.

[0343] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ152.5,151.2,149.8,138.1,136.8,126.0,122.4,119.6,84.3,24.9ppm.

[0344] 11 B{ 1 H}NMR (128 MHz, CDCl 3 )δ29.1ppm.

[0345] Embodiment 34

[0346] The method for synthesizing aromatic borate esters by selective boronation of aromatic compounds of the present invention is connected in series with the Suzuki-Miyaura coupling reaction to synthesize 2-(naphthalene-1-yl)pyridine: In a glove box filled with argon, 10 mL of Add 56.0 mg (0.5 mmol) of potassium tert-butoxide, 116.0 mg (0.5 mmol) of 4,4,5,5-tetramethyl-2-(1-phenylethyl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to the Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 41.4 mg (0.2 mmol) of 1-bromonaphthalene to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 5 hours; after the boronization process is completed, add 5.8 mg (0.05 mmol) of tetrakis(triphenylphosphine)palladium, 47.4 mg (0.3 mmol) of 2-bromopyridine and degassed water (0.5 mL) directly to the reaction mixture in a glove box filled with argon. Seal the reaction tube, take it out of the glove box and stir it at 120°C for 12 hours. After the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated saline to the reaction vessel to quench it, and extract it with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 50:1) was purified to obtain 23.0 mg of yellow oily liquid with a yield of 56%. The reaction route involved is as follows:

[0347]

[0348] The product characterization data are as follows:

[0349]

[0350] 1 H NMR (400 MHz, CDCl 3 )δ8.81(ddd,J=4.9,1.8,0.9Hz,1H),8.13–8.06(m,1H),7.95–7.89(m,2H),7.82(td,J=7. 7,1.8Hz,1H),7.64–7.54(m,3H),7.53–7.46(m,2H),7.33(ddd,J=7.6,4.9,1.2Hz,1H)ppm.

[0351] 13 C{ 1 H}NMR (101 MHz, CDCl 3)δ159.4,149.6,138.6,136.5,134.0,131.3,129.0,128.5,127.6,126.6,126.0,125.7,125.4,125.2,122.1ppm.

[0352] Embodiment 35

[0353] The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds of the present invention is connected in series with the Suzuki-Miyaura coupling reaction to synthesize 2-(2,4,6-trimethylphenyl)pyridine: In a glove box filled with argon, 10 mL of Add 48.0 mg (0.5 mmol) of sodium tert-butoxide, 116.0 mg (0.5 mmol) of 4,4,5,5-tetramethyl-2-(1-phenylethyl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to the Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 39.8 mg (0.2 mmol) of 2-bromo-1,3,5-trimethylbenzene to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 5 hours; after the boronization process is completed, add 5.8 mg (0.05 mmol) of tetrakis(triphenylphosphine)palladium, 47.4 mg (0.3 mmol) of 2-bromopyridine and degassed water (0.5 mL) directly to the reaction mixture in a glove box filled with argon. Seal the reaction tube, take it out of the glove box and stir it at 120°C for 12 hours. After the reaction was completed, 3 mL of saturated ammonium chloride solution and 1 mL of saturated saline were added to the reaction vessel to quench, and the mixture was extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 50:1) to obtain 16.0 mg of yellow oily liquid with a yield of 41%. The reaction route involved is as follows:

[0354]

[0355] The product characterization data are as follows:

[0356]

[0357] 1 H NMR (400 MHz, CDCl 3 )δ8.70(ddd,J=4.9,1.9,1.0Hz,1H),7.73(td,J=7.7,1.8Hz,1H),7.25–7.20(m,2H),6.92(s,2H),2.32(s,3H),2.01(s,6H)ppm.

[0358] 13C{ 1 H}NMR (101 MHz, CDCl 3 )δ160.2,149.7,137.8,137.5,136.3,135.8,128.4,124.8,121.6,21.2,20.2ppm.

[0359] Embodiment 36

[0360] The method for synthesizing aromatic borate esters by selective boronization of aromatic hydrocarbon compounds of the present invention is connected in series with the Suzuki-Miyaura coupling reaction to synthesize N,N-dimethyl-4-(pyridin-2-yl)aniline: In a glove box filled with argon, 10 mL of Add 48.0 mg (0.5 mmol) of sodium tert-butoxide, 116.0 mg (0.5 mmol) of 4,4,5,5-tetramethyl-2-(1-phenylethyl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to the Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 40.0 mg (0.2 mmol) of 4-bromo-N,N-dimethylaniline to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 5 hours; after the boronization process is completed, add 5.8 mg (0.05 mmol) of tetrakis(triphenylphosphine)palladium, 47.4 mg (0.3 mmol) of 2-bromopyridine and degassed water (0.5 mL) directly to the reaction mixture in a glove box filled with argon. Seal the reaction tube, take it out of the glove box and stir it at 120°C for 12 hours. After the reaction was completed, 3 mL of saturated ammonium chloride solution and 1 mL of saturated saline were added to the reaction vessel to quench, and the mixture was extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 50:1) to obtain 33.5 mg of yellow solid with a yield of 85%. The reaction route involved is as follows:

[0361]

[0362] The product characterization data are as follows:

[0363]

[0364] 1 H NMR (400 MHz, CDCl 3 )δ8.62(dt,J=4.8,1.6Hz,1H),7.92(d,J=9.0Hz,2H),7.69–7.62(m,2H),7.09(ddd,J=6.2,4.9,2.4Hz,1H),6.80(d,J=9.0Hz,2H),3.01(s,6H)ppm.

[0365] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ157.7,151.2,149.5,136.6,127.8,127.3,120.7,119.2,112.3,40.5ppm.

[0366] Embodiment 37

[0367] The method for synthesizing aromatic borate esters by selective boronation of aromatic compounds of the present invention is connected in series with the Suzuki-Miyaura coupling reaction to synthesize 2-(4-methoxyphenyl)pyridine: In a glove box filled with argon, 10 mL of Add 56.0 mg (0.5 mmol) of potassium tert-butoxide, 116.0 mg (0.5 mmol) of 4,4,5,5-tetramethyl-2-(1-phenylethyl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to the Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 37.4 mg (0.2 mmol) of 4-bromoanisole to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 5 hours; after the boronization process is completed, in a glove box filled with argon, directly add 5.8 mg (0.05 mmol) of tetrakis(triphenylphosphine)palladium, 47.4 mg (0.3 mmol) of 2-bromopyridine and degassed water (0.5 mL) to the reaction mixture. Seal the reaction tube, take it out of the glove box and stir it at 120°C for 12 hours. After the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated saline to the reaction vessel to quench it, and extract it with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 50:1 to 25:1 to petroleum ether: dichloromethane = 1:1) to obtain 25.9 mg of a white solid with a yield of 70%. The reaction route involved is as follows:

[0368]

[0369] The product characterization data are as follows:

[0370] 1 H NMR (400 MHz, CDCl 3 )δ8.65(ddd,J=4.9,1.8,1.0Hz,1H),7.97–7.92(m,2H),7.73–7.63(m,2H),7.16(ddd,J=7.2,4.8,1.5Hz,1H),7.04–6.95(m,2H),3.86(s,3H)ppm.

[0371] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ160.6,157.3,149.7,136.8,132.2,128.3,121.5,119.9,114.3,55.5ppm.

[0372] Embodiment 38

[0373] The method for synthesizing aromatic borate esters by selective boronation of aromatic compounds of the present invention is connected in series with the Suzuki-Miyaura coupling reaction to synthesize 2-[4-(trifluoromethyl)phenyl]pyridine: In a glove box filled with argon, 10 mL of Add 56.0 mg (0.5 mmol) of potassium tert-butoxide, 116.0 mg (0.5 mmol) of 4,4,5,5-tetramethyl-2-(1-phenylethyl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to the Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 45.0 mg (0.2 mmol) of 4-bromotrifluorotoluene to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 5 hours; after the boronization process is completed, in a glove box filled with argon, directly add 5.8 mg (0.05 mmol) of tetrakis(triphenylphosphine)palladium, 47.4 mg (0.3 mmol) of 2-bromopyridine and degassed water (0.5 mL) to the reaction mixture. Seal the reaction tube, take it out of the glove box and stir it at 120°C for 12 hours. After the reaction is completed, add 3 mL of saturated ammonium chloride solution and 1 mL of saturated saline to the reaction vessel to quench it, and extract it with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 39.4 mg of white solid with a yield of 88%. The reaction route involved is as follows:

[0374]

[0375] The product characterization data are as follows:

[0376]

[0377] 1 H NMR (400 MHz, CDCl 3 )δ8.72(dt,J=4.9,1.4Hz,1H),8.11(d,J=8.1Hz,2H),7.83–7.70(m,4H),7.29(ddd,J=6.8,4.8,1.7Hz,1H)ppm.

[0378] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ156.0,150.1,142.8,137.1,130.9(q,J=32.2Hz),127.3,125.8(q,J=3.8Hz),124.3(d,J=272.2Hz),123.1,121.0ppm.

[0379] 19 F{ 1 H}NMR (376MHz, CDCl 3 )δ-62.6ppm.

[0380] Embodiment 39

[0381] The method for synthesizing aromatic borate esters by selective boronation of aromatic compounds of the present invention is connected in series with the Suzuki-Miyaura coupling reaction to synthesize N,N-diethyl-4-(pyridin-2-yl)benzamide: In a glove box filled with argon, 10 mL of Sodium tert-butoxide 48.0 mg (0.5 mmol), 4,4,5,5-tetramethyl-2-(1-phenylethyl)-1,3,2-dioxaborolane 116.0 mg (0.5 mmol), and tetrahydrofuran 1 mL were added to the Schlenk tube, and stirred at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; N,N-diethyl-4-bromobenzamide 51.2 mg (0.2 mmol) was added to the above reaction solution, and the mixture was sealed and removed from the glove box, and stirred at 80°C for 5 hours; after the boronization process was completed, tetrakis(triphenylphosphine)palladium 5.8 mg (0.05 mmol), 2-bromopyridine 47.4 mg (0.3 mmol) and degassed water (0.5 mL) were directly added to the reaction mixture in a glove box filled with argon. The reaction tube was sealed and taken out of the glove box and stirred at 120°C for 12 hours. After the reaction was completed, 3 mL of saturated ammonium chloride solution and 1 mL of saturated saline were added to the reaction vessel to quench, and the mixture was extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 5:1 to petroleum ether: acetone = 5:1) to obtain 23.5 mg of yellow oily liquid with a yield of 46%. The reaction route involved is as follows:

[0382]

[0383] The product characterization data are as follows:

[0384]

[0385] 1 1H NMR (400 MHz, CDCl 3 ) δ 8.69 (dt, J = 4.9, 1.4 Hz, 1H), 8.00 (d, J = 8.3 Hz, 2H), 7.79–7.69 (m, 2H), 7.47 (d, J = 8.3 Hz, 2H), 7.24 (td, J = 5.0, 2.5 Hz, 1H), 3.55 (s, 2H), 3.27 (s, 2H), 1.24 (s, 3H), 1.10 (s, 3H). ppm.

[0386] 13 13C{ 1 1H} NMR (101 MHz, CDCl 3 ) δ 171.1, 156.8, 149.9, 140.2, 137.8, 137.0, 127.1, 126.9, 122.6, 120.8, 43.4, 39.4, 14.3, 13.0 ppm.

[0387] HRMS (ESI): calculated for C 16 16 19 11 2 1 + [M + H] + 255.1492; found 255.1484.

[0388] Example 40

[0389] The method for synthesizing aromatic borate esters by selective boronation of aromatic hydrocarbon compounds of the present invention is connected in series with the Suzuki-Miyaura coupling reaction to synthesize 2-(benzofuran-7-yl)pyridine: In a glove box filled with argon, 10 mL of Add 48.0 mg (0.5 mmol) of sodium tert-butoxide, 116.0 mg (0.5 mmol) of 4,4,5,5-tetramethyl-2-(1-phenylethyl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to the Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 39.4 mg (0.2 mmol) of 7-bromobenzofuran to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 5 hours; after the boronization process is completed, add 5.8 mg (0.05 mmol) of tetrakis(triphenylphosphine)palladium, 47.4 mg (0.3 mmol) of 2-bromopyridine and degassed water (0.5 mL) directly to the reaction mixture in a glove box filled with argon. Seal the reaction tube, take it out of the glove box and stir it at 120°C for 12 hours. After the reaction was completed, 3 mL of saturated ammonium chloride solution and 1 mL of saturated saline were added to the reaction vessel to quench, and the mixture was extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 34.7 mg of yellow oily liquid with a yield of 89%. The reaction route involved is as follows:

[0390]

[0391] The product characterization data are as follows:

[0392] 1 H NMR (400 MHz, CDCl 3 )δ8.76(ddd,J=4.8,1.9,1.0Hz,1H),8.26(dt,J=8.0,1.1Hz,1H),8.10(dd,J=7.7,1.3Hz,1H),7.80(td,J=7.8,1.9Hz,1H),7.71( d,J=2.2Hz,1H),7.65(dd,J=7.7,1.3Hz,1H),7.38(t,J=7.7Hz,1H),7.25(ddd,J=7.4,4.8,1.1Hz,1H),6.84(d,J=2.2Hz,1H)ppm.

[0393] 13 C{ 1 H}NMR (101 MHz, CDCl 3)δ154.1,152.5,149.8,145.0,136.7,128.6,124.5,124.1,124.0,123.5,122.4,122.2,106.9ppm.

[0394] HRMS(ESI):calculated for C 13 H 10 NO + [M+H] + 196.0757; found 196.0756.

[0395] Embodiment 41

[0396] The method for synthesizing aromatic borate esters by selective boronation of aromatic compounds of the present invention is connected in series with the Suzuki-Miyaura coupling reaction to synthesize 2-(dibenzo[b,d]thiophen-2-yl)pyridine: In a glove box filled with argon, 10 mL of Add 48.0 mg (0.5 mmol) of sodium tert-butoxide, 116.0 mg (0.5 mmol) of 4,4,5,5-tetramethyl-2-(1-phenylethyl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to the Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 52.6 mg (0.2 mmol) of 2-bromodibenzothiophene to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 5 hours; after the boronization process is completed, add 5.8 mg (0.05 mmol) of tetrakis(triphenylphosphine)palladium, 47.4 mg (0.3 mmol) of 2-bromopyridine and degassed water (0.5 mL) directly to the reaction mixture in a glove box filled with argon. Seal the reaction tube, take it out of the glove box and stir it at 120°C for 12 hours. After the reaction was completed, 3 mL of saturated ammonium chloride solution and 1 mL of saturated saline were added to the reaction vessel to quench, and the mixture was extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product. The crude product was subjected to preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 40.6 mg of yellow oily liquid with a yield of 78%. The reaction route involved is as follows:

[0397]

[0398] The product characterization data are as follows:

[0399]

[0400] 1 H NMR (400 MHz, CDCl 3)δ8.82(d,J=1.7Hz,1H),8.75(ddd,J=4.9,1.8,1.0Hz,1H),8.31–8.26(m,1H),8.07(dd,J=8.4,1.8Hz,1H),7. 92(d,J=8.4Hz,1H),7.88–7.80(m,2H),7.77(dd,J=7.8,1.8Hz,1H),7.50–7.44(m,2H),7.27–7.22(m,1H)ppm.

[0401] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ157.4,149.8,140.4,139.9,137.0,136.2,136.1,135.7,127.0,125.6,124.6,123.0,123.0,122.2,122.0,120.7,120.1ppm.

[0402] Embodiment 42

[0403] The method for synthesizing aromatic borate esters by selective boronation of aromatic compounds of the present invention is connected in series with the Suzuki-Miyaura coupling reaction to synthesize 2-(dibenzo[b,d]furan-2-yl)pyridine: In a glove box filled with argon, 10 mL of Add 48.0 mg (0.5 mmol) of sodium tert-butoxide, 116.0 mg (0.5 mmol) of 4,4,5,5-tetramethyl-2-(1-phenylethyl)-1,3,2-dioxaborolane, and 1 mL of tetrahydrofuran to the Schlenk tube, and stir at room temperature (20°C) for 10 min to obtain an activated carbon negative intermediate reaction solution; add 49.4 mg (0.2 mmol) of 2-bromodibenzofuran to the above reaction solution, seal it and move it out of the glove box, and stir it at 80°C for 5 hours; after the boronization process is completed, add 5.8 mg (0.05 mmol) of tetrakis(triphenylphosphine)palladium, 47.4 mg (0.3 mmol) of 2-bromopyridine and degassed water (0.5 mL) directly to the reaction mixture in a glove box filled with argon. Seal the reaction tube, take it out of the glove box and stir it at 120°C for 12 hours. After the reaction was completed, 3 mL of saturated ammonium chloride solution and 1 mL of saturated brine were added to the reaction vessel to quench, and the mixture was extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product, which was purified by preparative thin layer chromatography (solid phase silica gel 60F 254 , mobile phase petroleum ether: ethyl acetate = 100: 1) to obtain 46.6 mg of white solid, with a yield of 95%. The reaction route involved is as follows:

[0404]

[0405] The product characterization data are as follows:

[0406]

[0407] 1 H NMR (400 MHz, CDCl 3 )δ8.72(ddd,J=4.8,1.8,1.0Hz,1H),8.61(dd,J=1.9,0.6Hz,1H),8.06(dd,J =8.6,1.9Hz,1H),8.01(ddd,J=7.6,1.4,0.7Hz,1H),7.80–7.72(m,2H),7.62 (dd,J=8.7,0.6Hz,1H),7.57(dt,J=8.3,0.9Hz,1H),7.46(ddd,J=8.3,7.2,1 .4Hz,1H),7.35(td,J=7.5,1.0Hz,1H),7.22(ddd,J=7.2,4.9,1.5Hz,1H)ppm.

[0408] 13 C{ 1 H}NMR (101 MHz, CDCl 3 )δ157.5,156.92,156.85,149.8,137.0,134.6,127.5,126.4,124.9,124.4,123.0,122.0,121.0,120.7,119.5,111.9,111.8ppm.

[0409] Comparative Example 1

[0410] On the basis of Example 3, 38.3 mg (0.3 mmol) of pinacol borane was used to replace 4,4,5,5-tetramethyl-2-(2-phenylpropan-2-yl)-1,3,2-dioxaborolane, and 33.7 mg (0.3 mmol) of potassium tert-butoxide and 26.2 mg (0.2 mmol) of N-methylindole were reacted in tetrahydrofuran solvent. The reaction steps were the same as those in Example 3. The synthetic route was as follows:

[0411]

[0412] It was detected that no target product, aryl borate, was generated. Therefore, the boron reagent in the method of the present invention has a role in the reaction that cannot be replaced by traditional borane reagents.

Claims

1. A method for synthesizing aromatic borate esters by selective boronization of aromatic compounds, characterized in that: The following steps are involved: (1) adding a boron reagent A to an organic solvent to react under the action of an organic strong base to obtain an active boron species and a carbon anion intermediate reaction solution; (2) adding an aromatic compound Ar-X to the reaction solution of step (1) to carry out a borylation reaction to obtain an aromatic borate ester product; the borylation reaction temperature is 60 to 100° C.; The synthetic route is as follows: Among them, R1 is a benzene ring, a C1-C5 alkenyl group or a borate group, R2 is a C1-C5 alkyl group or H; R3 is a C1-C5 alkyl group or H; X is H or a halogen.

2. The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds according to claim 1, characterized in that: The R2 is methyl or H, and R3 is methyl or H.

3. The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds according to claim 1, characterized in that: The R1 is a benzene ring, R2 is a methyl group or H, and R3 is a methyl group or H.

4. The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds according to claim 1, characterized in that: The R1 is a C1-C5 alkenyl group, R2 is a methyl group or H, and R3 is a methyl group or H.

5. The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds according to claim 1, characterized in that: The R1 is a borate group, R2 is a methyl group or H, and R3 is a methyl group or H.

6. The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds according to claim 1, characterized in that: The boron reagent A is:

7. The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds according to claim 1, characterized in that: The boronization reaction temperature is 80-100°C.

8. The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds according to claim 1, characterized in that: The molar ratio of the boron reagent: the organic strong base: the aromatic compound is 1 to 3:1 to 3:

1.

9. The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds according to claim 1, characterized in that: The aromatic compound Ar-X is selected from N-methylindole, N-ethylindole, N-phenylindole, 1,3-dimethylindole, 1,4-dimethylindole, 1,5-dimethylindole, 1,6-dimethylindole, 1,7-dimethylindole, 5-methoxy-1-methyl-1H-indole, 5-fluoro-1-methyl-1H-indole, 5-chloro-1-methyl-1H-indole, 1-methyl-5-trifluoromethyl-1H-indole, 1-methyl-7-azaindole, dibenzothiophene, dibenzofuran, N-methylpyrrole, diphenyl ether, 1 , 4-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, 1-fluoro-4-methoxybenzene, benzothiophene, 5-bromobenzothiophene, benzofuran, 2-n-pentylthiophene, 2-n-pentylfuran, 2-(2-thiophene)pyridine, dithiophene, 3,4-ethylenedioxythiophene, 1-bromonaphthalene, 4-bromo-N,N-dimethylaniline, 4-bromoanisole, 2-bromo-1,3,5-trimethylbenzene, 4-bromotrifluorotoluene, N,N-diethyl-4-bromobenzamide, 7-bromobenzofuran, 2-bromodibenzothiophene or 2-bromodibenzofuran.

10. The method for synthesizing aromatic borate esters by selective boronization of aromatic compounds according to claim 1, characterized in that: The organic solvent is selected from one or more of tetrahydrofuran, 1,4-dioxane, cyclohexane and toluene.

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