A method for preparing a diboronate-based arene compound

Abstract

The application provides a preparation method of a diboronate-based aromatic compound, and relates to organic synthesis. The application uses aryl halide and pinacol diboron as raw materials, and under the action of a titanium catalyst and an alkaline reagent, a diboronate-based aromatic compound can be efficiently prepared through one-step reaction. The preparation method provided by the application can realize selective preparation of 1,2-diboronate-based aromatic compounds, 1,3-boronate-based aromatic compounds and 1,4-boronate-based aromatic compounds, and has the advantages of simple preparation process, convenient operation, wide applicability to various aryl halides, wide applicability of functional groups and universality. The application does not need to use a noble metal catalyst and a phosphine ligand, and uses a titanium catalyst which is widely available and low in cost, so that the production cost of the diboronate-based aromatic compound is greatly reduced.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, and specifically to a method for preparing diboron ester-based aromatic compounds. Background Technology

[0002] Arylboronic acids possess advantages such as high stability, low toxicity, and ease of handling, making them widely used in organic synthesis, pharmaceuticals, and the synthesis of bioactive natural products. Furthermore, arylboronic acids can also be used as sensors for carbohydrates, enzyme inhibitors, and transport carriers for nucleosides and sugars. Therefore, developing efficient and mild synthetic methods for arylboronic acids has always been a key focus for chemists.

[0003] Currently, the main methods for preparing arylboronic esters include the synthesis of arylboronic esters from aryl Grignard or lithium reagents and boron electrophilic reagents, the catalytic boration of aryl halides, and the boration of CH bonds in aromatic hydrocarbons. However, the above research focuses on the synthesis of monoborated aromatic hydrocarbons. Further introducing multiple borate groups onto the aromatic ring would not only provide a richer source of raw materials for organic synthesis chemistry but also greatly expand the application range of arylboronic esters. In addition, some aryl polyboronic esters can also serve as electron transport materials for fluorescence and optoelectronic applications. However, the synthetic methods for aryl polyboronic esters are very limited; in most cases, aryl polyboronic esters are generated as byproducts, and their synthesis and application research are still in their infancy. Therefore, developing selective and efficient methods for the synthesis of polyborated aromatic hydrocarbons is of great significance. Summary of the Invention

[0004] In view of this, the object of the present invention is to provide a method for preparing diboronate aromatic compounds. The preparation method provided by the present invention can achieve efficient preparation of diboronate aromatic compounds, and can selectively prepare 1,2-diboronate aromatic compounds, 1,3-boronate aromatic compounds, and 1,4-boronate aromatic compounds.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a method for preparing diboron ester-based aromatic compounds, comprising the following steps:

[0007] Under a protective atmosphere, aryl halides, pinacol diboronic acid esters, titanium catalysts, basic reagents, and solvents are mixed and subjected to a substitution reaction to obtain diboronic acid ester aromatic compounds.

[0008] Preferably, the molar ratio of the aryl halide to pinacol diboronic acid ester is 1:2 to 5.

[0009] Preferably, the aryl group in the aryl halide includes indolyl, pyrroleyl, tetrahydronaphthyl, benzodioxane, piperonyl, naphthyl, phenyl, substituted phenyl or substituted naphthyl; the halogen in the aryl halide includes one or more of fluorine, chlorine, bromine and iodine.

[0010] Preferably, the substituents in the substituted phenyl and substituted naphthyl groups independently include one or more of the following: halogen, C1-C4 alkyl, phenyl, benzyl, methoxy, benzylmethoxy, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methylthio, N,N-dimethyl, trimethylsilyl, tert-butyldimethylsiloxy, pinacol boronic acid ester, methyloxymethyl, pyrrolyl, and morpholinyl.

[0011] Preferably, the molar ratio of the aryl halide to the titanium catalyst is 1:0.025 to 0.2.

[0012] Preferably, the titanium catalyst comprises a titanium complex.

[0013] Preferably, the titanium complex comprises titanium dichlorodicyclopentadiene and / or Rosenthal Ti, wherein the structural formula of Rosenthal Ti is as follows:

[0014] Preferably, the alkaline reagent comprises metal alkoxides and / or carbonates;

[0015] The molar ratio of the aryl halide to the basic reagent is 1:0.25 to 2.

[0016] Preferably, the solvent includes ether solvents and / or benzene solvents.

[0017] Preferably, the substitution reaction is carried out at a temperature of 25–120°C for a time of 15–30 h.

[0018] This invention utilizes aryl halides and pinacol diboronic acid esters as raw materials to efficiently prepare diboronic acid ester-based aromatic compounds in a single step under the action of a titanium catalyst and a basic reagent. The preparation method provided by this invention, through control of the reaction substrate (aryl halides), enables the selective preparation of 1,2-diboronic acid ester-based aromatic compounds, 1,3-boronic acid ester-based aromatic compounds, and 1,4-boronic acid ester-based aromatic compounds. The preparation process is simple, easy to operate, applicable to a variety of aryl halides, has a wide range of functional groups, and the preparation method is universal.

[0019] This invention eliminates the need for precious metal catalysts and phosphine ligands, and utilizes titanium catalysts which are widely available and inexpensive, significantly reducing the production cost of diboron ester-based aromatic compounds.

[0020] Furthermore, this invention enables the high chemoselectivity of diboronate aromatic compounds with various functional substituents (aryl and halogen) under mild conditions, and the prepared diboronate aromatic compounds can be widely used in organic synthesis, pharmaceutical and active natural product synthesis. Detailed Implementation

[0021] This invention provides a method for preparing diboron ester-based aromatic compounds, comprising the following steps: under a protective atmosphere, mixing an aryl halide, pinacol diboronate, a titanium catalyst, a basic reagent, and a solvent to carry out a substitution reaction to obtain diboron ester-based aromatic compounds.

[0022] Unless otherwise specified, the materials and equipment used in this invention are all commercially available products in the field.

[0023] In this invention, the aryl group in the aryl halogen preferably includes indolyl, pyrroleyl, tetrahydronaphthyl, benzodioxane, piperonyl, naphthyl, phenyl, substituted phenyl or substituted naphthyl; the halogen in the aryl halogen preferably includes one or more of fluorine, chlorine, bromine and iodine, more preferably fluorine, chlorine, bromine or iodine.

[0024] In this invention, the substituents in the substituted phenyl and substituted naphthyl groups preferably include one or more of halogens, C1-C4 alkyl groups, phenyl groups, benzyl (-Bn), methoxy (-OMe), benzyl methoxy (-OBn), trifluoromethyl (-CF3), trifluoromethoxy (-OCF3), trifluoromethylthio (-SCF3), methylthio (-SMe), N,N-dimethyl (-NMe2), trimethylsilyl (-SiMe3), tert-butyldimethylsiloxy, pinacol boronic acid ester (-Bpin), methyloxymethyl (-CH2OMe), pyrroleyl, and morpholinyl. In this invention, the halogen preferably includes one or more of fluorine, chlorine, bromine, and iodine. In this invention, the C1-C4 alkyl group preferably includes one or more of methyl (-Me), ethyl (-Et), propyl, and butyl; the propyl group preferably includes n-propyl and / or isopropyl (…). i Pr); the butyl group preferably includes n-butyl(- n Bu), sec-butyl (- i Bu), isobutyl (- s Bu) and tert-butyl t One or more of the following: Bu; when the substituent is two or more substituents, it preferably includes 2,3-dimethyl, 3,4-dimethyl, 3,5-dimethyl, 3,6-dimethyl, 1,3,5-trimethyl, 1,3,4,6-tetramethyl, 3,5-dimethyl-4-methoxy, or 2-methyl-3-fluoro.

[0025] In this invention, the aryl halogens preferably include p-bromotoluene, bromobenzene, 4-bromobiphenyl, 4-bromodiphenylmethane, 4-bromoanisole, 4-bromoanisole, 4-bromo-N,N-dimethylaniline, 4-benzyloxybromobenzene, p-fluorobromobenzene, p-chlorobromobenzene, p-trifluoromethylbromobenzene, p-bromotrifluoromethoxybenzene, p-bromotrifluoromethylthiobenzene, 1-bromo-4-trimethylsilylbenzene, (4-bromophenoxy)tert-butyldimethylsilane, pinacol ester of 4-bromophenylboronic acid, 2-bromotoluene, 2-bromoethylbenzene, 1-bromo-2-isopropylbenzene, 1-bromo-3-(methoxymethyl)benzene, 2,3-dimethylbromobenzene, 4-bromo-2,6-dimethylanisole, 2-bromonaphthalene, 1 6-Bromonaphthalene, 6-Bromo-1,2,3,4-Tetrahydronaphthalene, 6-Bromo-1,4-Benzoxane, 4-Bromo-1,2-Methylenedioxybenzene, 5-Bromo-1-Methyl-1H-indole, 1-(4-Bromophenyl)pyrrole, m-Bromoanisole, 2-Bromo-1,3,5-Trimethylbenzene, 1-Bromo-2,3,5,6-Tetramethylbenzene, 4-Iodotoluene, 4-Iodoanisole, 1-Iodo-3,4-Methylenedioxybenzene, 4-(4-Iodophenyl)morpholine, 1-tert-butyl-4-iodobenzene, 4-Chloroanisole, 3-Chloro-o-xylene, 2-Chloro-6-fluorotoluene, 3,5-Dimethylchlorobenzene, 2-Chloro-1,4-Dimethylbenzene, or 4-tert-butylchlorobenzene.

[0026] In this invention, the molar ratio of the aryl halide to pinacol diboronic acid is preferably 1:2 to 5, and in specific embodiments it can be 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5.

[0027] In this invention, the structural formula of the pinacol diboronate (B2pin2) is as follows:

[0028] In this invention, the titanium catalyst preferably comprises a titanium complex; the titanium complex preferably comprises titanium dichlorodichlorocaprocene and / or Rosenthal Ti, wherein the structural formula of Rosenthal Ti is as follows: In this invention, the molar ratio of the aryl halide to the titanium catalyst is preferably 1:0.025 to 0.2, and in specific embodiments it can be 1:0.025, 1:0.05, 1:0.08, 1:0.1, 1:0.12, 1:0.15, 1:0.18 or 1:0.2.

[0029] In this invention, the alkaline reagent preferably comprises a metal alkoxide and / or a carbonate. The metal alkoxide preferably comprises an alkali metal alkoxide, and in specific embodiments may be one or more of lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, lithium tert-butoxide, sodium tert-butoxide, and potassium tert-butoxide. The carbonate preferably comprises an alkali metal carbonate, and in specific embodiments may be one or more of sodium carbonate, potassium carbonate, and cesium carbonate. The molar ratio of the aryl halide to the alkaline reagent is preferably 1:0.25 to 2, and in specific embodiments may be 1:0.25, 1:0.5, 1:0.8, 1:1, 1:1.2, 1:5, 1:1.8, or 1:2.

[0030] In this invention, the solvent preferably includes ether solvents and / or benzene solvents; the ether solvent preferably includes methyl tert-butyl ether and / or tetrahydrofuran; the benzene solvent preferably includes benzene and / or toluene. In this invention, the molar ratio of the aryl halide to the volume of the solvent is preferably 1 mol: 1 to 10 L, and in specific embodiments it can be 1 mol: 1 L, 1 mol: 3 L, 1 mol: 5 L, 1 mol: 8 L or 1 mol: 10 L.

[0031] In this invention, the protective atmosphere preferably includes nitrogen or an inert gas, and the inert gas preferably includes argon or helium; the pressure of the protective atmosphere is preferably 1 atmosphere.

[0032] The present invention does not have any special limitation on the mixing. Any mixing method known to those skilled in the art can be used to mix the raw materials evenly, such as stirring.

[0033] In this invention, the temperature of the substitution reaction is preferably 25–120°C, and in specific embodiments it can be 25°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C or 120°C; the time of the substitution reaction is preferably 15–30 h, and in specific embodiments it can be 15 h, 18 h, 20 h, 22 h, 24 h, 25 h, 28 h or 30 h; the substitution reaction is preferably carried out under stirring conditions.

[0034] In this invention, the diboronate aromatic compounds preferably include one or more of 1,2-diboronate aromatic compounds, 1,3-boronate aromatic compounds, and 1,4-boronate aromatic compounds, more preferably 1,2-diboronate aromatic compounds, 1,3-boronate aromatic compounds, or 1,4-boronate aromatic compounds.

[0035] The present invention does not have any particular limitation on the container used for the mixing and substitution reaction; any reaction container known to those skilled in the art can be used, such as a pressure-resistant tube.

[0036] After the substitution reaction is completed, the present invention preferably further includes: concentrating the reaction solution obtained from the substitution reaction, mixing the crude product, trimethylamine N-oxide and acetonitrile (as a process to remove unreacted residual pinacol diboronic acid ester), and purifying by column chromatography to obtain diboronic acid ester aromatic compounds.

[0037] The present invention does not have any special limitations on the concentration method; any concentration method known to those skilled in the art that can completely remove the solvent is acceptable.

[0038] In this invention, the trimethylamine N-oxide preferably comprises trimethylamine N-oxide dihydrate. In this invention, the molar ratio of the aryl halide to the trimethylamine N-oxide is preferably 1:3 to 5, and in specific embodiments it can be 1:3, 1:3.5, 1:4, 1:4.5, or 1:5.

[0039] In this invention, the preferred molar ratio of the aryl halide to the volume of acetonitrile is 1 mol: 10-20 L. In specific embodiments, it can be 1 mol: 10 L, 1 mol: 12 L, 1 mol: 15 L, 1 mol: 18 L or 1 mol: 20 L.

[0040] In this invention, the mixing temperature is preferably 10-30°C, and in specific embodiments it can be 10°C, 15°C, 20°C, 25°C or 30°C; the mixing time is preferably 0.5-2h, and in specific embodiments it can be 0.5h, 1h, 1.5h or 2h.

[0041] In this invention, the eluent used for column chromatography purification preferably includes petroleum ether and ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate is preferably 2 to 10:1. In specific embodiments, it can be 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1. The diboronate aromatic compounds prepared by this invention have a tailing characteristic. The eluent used in this invention has low polarity, which enables rapid column chromatography separation of diboronate aromatic compounds.

[0042] To further illustrate the present invention, the preparation method of the diboronate ester aromatic compounds provided by the present invention will be described in detail below with reference to the embodiments, but these should not be construed as limiting the scope of protection of the present invention.

[0043] In the following examples, the titanium catalyst is Rosenthal Ti.

[0044] Example 1

[0045]

[0046] In a nitrogen-filled glove box, p-bromotoluene (denoted as 1a, 0.2 mmol, 34.2 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed. The crude product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for another 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound with the structure shown in 3a (white solid, 2,2'-(4-methyl-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in 63% yield.

[0047] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.57(d,J=7.6Hz,1H),7.45(s,1H),7.20-7.16(m,1H),2.32(s,3H),1.37(s,12H),1.35(s,12H). 13 C NMR (101MHz, CDCl3) δ138.9,134.1,133.9,129.8,83.8,83.7,24.92,24.90,21.5. 11 BNMR(128MHz,CDCl3)δ31.40.HRMS(ESI)m / z:[M+Na] + Calcd for C 19 H 30 B2O4Na + 367.2222; Found 367.2227.

[0048] Example 2

[0049]

[0050] In a nitrogen-filled glove box, bromobenzene (denoted as 1b, 0.2 mmol, 31.4 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed. The crude product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for another 1 h. Then, column chromatography was performed for purification (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diborate ester-based aromatic compound (white solid, 1,2-bis(4,4,5,5-tetramethyl-1,3,2-dioxoboron-2-yl)benzene) with the structure shown in 3b, in a yield of 53%.

[0051] The product characterization data are as follows: 1 HNMR (400MHz, CDCl3) δ7.64 (dd, J=5.5, 3.3Hz, 2H), 7.37 (tt, J=4.6, 2.4Hz, 2H), 1.37 (s, 24H). 13 C NMR (101MHz, CDCl3) δ133.5,129.2,83.9,24.9. 11 B NMR(128MHz,CDCl3)δ31.82.HRMS(ESI)m / z:[M+Na] + Calcd for C 21 H 34 B2O4Na + 353.2066; Found 353.2069.

[0052] Example 3

[0053]

[0054] In a nitrogen-filled glove box, 4-bromobiphenyl (denoted as 1c, 0.2 mmol, 46.6 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product and trimethylolpropionate were collected. Methylamine N-oxide dihydrate (0.9 mmol, 100 mg) was placed in acetonitrile (2 mL) and reacted for 1 h. Then, it was purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound (white solid, 2,2'-([1,1'-biphenyl]-3,4-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) with the structure shown in 3c, in a yield of 56%.

[0055] The product characterization data are as follows: 1 H NMR(400MHz, CDCl3) δ7.88(d,J=1.6Hz,1H),7.77(d,J=7.7Hz,1H),7.65-7.61 (m,3H),7.44(t,J=7.6Hz,2H),7.34(t,J=7.3Hz,1H),1.40(d,J=2.7Hz,24H). 13 C NMR (101MHz, CDCl3) δ141.8,141.3,134.3,132.2,128.7,127.8,127.3,83.99,83.93,24.97,24.95. 11 B NMR(128MHz,CDCl3)δ31.57.HRMS(ESI)m / z:[M+Na] + Calcdfor C 24 H 32 B2O4Na + 429.2379; Found 429.2376.

[0056] Example 4

[0057]

[0058] In a nitrogen-filled glove box, 4-bromodiphenylmethane (denoted as 1d, 0.2 mmol, 49.4 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. The mixture was stirred at 40 °C for 24 h, after which the solvent was completely removed, and the crude... The product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 9:1) to give a diboronate ester aromatic compound with the structure shown in 3d (white solid, 2,2'-(4-benzyl-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in 42% yield.

[0059] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.59 (d, J = 7.6Hz, 1H), 7.53-7.48 (m, 1H), 7.25-7.21 (m, 2H), 7.1 7(dd,J=7.5,1.8Hz,2H),7.14-7.10(m,2H),3.97(s,2H),1.36(s,12H),1.35(s,12H). 13 C NMR (101MHz, CDCl3) δ141.8,141.1,134.2,133.9,130.0,128.9,128.3,125.9,83.9,83.8,41.9,24.9,24.8. 11 B NMR(128MHz,CDCl3)δ31.32.HRMS(ESI)m / z:[M+Na] + Calcd for C 25 H 34 B2O4Na + 443.2535; Found 443.2538.

[0060] Example 5

[0061]

[0062] In a nitrogen-filled glove box, 4-bromoanisole (denoted as 1e, 0.2 mmol, 37.4 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. The mixture was stirred at 40 °C for 24 h, after which the solvent was completely removed, and the crude product was... The compound and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 9:1) to give a diboronate ester aromatic compound (white solid, 2,2'-(4-methoxy-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) with the structure shown in 3e, in a yield of 56%.

[0063] The product characterization data are as follows: 1 HNMR (400MHz, CDCl3) δ7.66(d,J=8.3Hz,1H),7.11(d,J=2.6Hz,1H),6.89(dd,J=8.3,2.6Hz,1H),3.82(s,3H),1.38(s,12H),1.34(s,12H). 13 C NMR (101MHz, CDCl3) δ160.6,136.1,118.2,114.6,83.9,83.7,55.1,29.7,24.9,24.8. 11 B NMR(128MHz,CDCl3)δ31.06.HRMS(ESI)m / z:[M+Na] + Calcd for C 19 H 30 B2O5Na + 383.2172; Found 383.2172.

[0064] Example 6

[0065]

[0066] In a nitrogen-filled glove box, 4-bromoanisole (denoted as 1f, 0.2 mmol, 40.6 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product was collected. The trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) was placed in acetonitrile (2 mL) and reacted for 1 h. Then, it was purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 9:1) to give a diboronate ester aromatic compound (white solid, 2,2'-(4-(methylthio)-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) with the structure shown in 3f, in a yield of 51%.

[0067] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.60(d,J=7.9Hz,1H),7.48(d,J=1.7Hz,1H),7.24(dd,J=7.9,2.0Hz,1H),2.47(s,3H),1.35(s,24H). 13 CNMR (101MHz, CDCl3) δ140.3,134.3,130.9,126.6,84.0,83.8,24.9,24.8,15.4. 11 B NMR(128MHz,CDCl3)δ31.57.HRMS(ESI)m / z:[M+Na] + Calcd for C 19 H 30 B2O4SNa + 399.1943; Found 399.1945.

[0068] Example 7

[0069]

[0070] In a nitrogen-filled glove box, 4-bromo-N,N-dimethylaniline (1 g, 0.2 mmol, 40.0 mg), pinacol diborate (2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed. The crude product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. Then, the mixture was purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 4:1) to give 3 g of diboron ester aromatic compound with the structure shown (white solid, N,N-dimethyl-3,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxabor-2-yl)aniline), with a yield of 65%.

[0071] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.62(d,J=8.4Hz,1H),6.88(d,J=2.6Hz,1H),6.69(dd,J=8.4,2.6Hz,1H),2.96(s,6H),1.38(s,12H),1.32(s,12H). 13 C NMR (101MHz, CDCl3) δ151.2,136.0,116.4,112.5,83.6,83.2,40.2,24.9,24.8. 11 B NMR(128MHz,CDCl3)δ31.92.HRMS(ESI)m / z:[M+Na] + Calcd for C 20 H 33 B2O4NNa + 396.2488; Found 396.2479.

[0072] Example 8

[0073]

[0074] In a nitrogen-filled glove box, 4-benzyloxybromobenzene (denoted as 1h, 0.2 mmol, 52.6 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product was collected. The trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) was placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 9:1) to give a diboronate ester aromatic compound (white solid, 2,2'-(4-(benzyloxy)-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) with the structure shown in 3 h, in a yield of 35%.

[0075] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.62(d,J=8.4Hz,1H),6.88(d,J=2.6Hz,1H),6.69(dd,J=8.4,2.6Hz,1H),2.96(s,6H),1.38(s,12H),1.32(s,12H). 13 C NMR (101MHz, CDCl3) δ151.2,136.0,116.4,112.5,83.6,83.2,40.2,24.9,24.8. 11 B NMR(128MHz,CDCl3)δ31.92.HRMS(ESI)m / z:[M+Na] + Calcd for C 20 H 33 B2O4NNa + 396.2488; Found 396.2479.

[0076] Example 9

[0077]

[0078] In a nitrogen-filled glove box, p-fluorobromobenzene (denoted as 1i, 0.2 mmol, 35.0 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product was collected. The trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) was placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound (white solid, 2,2'-(4-fluoro-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) with the structure shown in 3i, in a yield of 23%.

[0079] The product characterization data are as follows: 1 HNMR (400MHz, CDCl3) δ7.67(dd,J=8.2,6.0Hz,1H),7.30(dd,J=9.5,2.6Hz,1H),7.05(td,J=8.7,2.7Hz,1H),1.37(s,12H),1.35(s,12H). 13 C NMR (101MHz, CDCl3) δ 163.8 (d, J = 251.1Hz), 136.2 (d, J = 7.3Hz), 119.9 (d, J = 18.8Hz), 116.0 (d, J = 19.9Hz), 84.11 (d, J = 18.2Hz), 24.9. 11 B NMR(128MHz,CDCl3)δ31.00.HRMS(ESI)m / z:[M+Na] + Calcd for C 18 H 27 B2O4FNa + 371.1972; Found 371.1976.

[0080] Example 10

[0081]

[0082] In a nitrogen-filled glove box, p-chlorobromobenzene (denoted as 1j, 0.2 mmol, 38.3 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product was collected. The trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) was placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound (white solid, 2,2'-(4-chloro-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) with the structure shown in 3j, in a yield of 31%.

[0083] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.60(s,2H),7.37-7.32(m,1H),1.37(s,12H),1.35(s,12H). 13 C NMR (101MHz, CDCl3) δ135.9,135.2,133.2,129.2,84.3,84.1,24.9. 11 B NMR(128MHz,CDCl3)δ31.16.HRMS(ESI)m / z:[M+Na] + Calcd for C 18 H 27 B2O4ClNa + 387.1676; Found 387.1681.

[0084] Example 11

[0085]

[0086] In a nitrogen-filled glove box, p-trifluoromethylbromobenzene (denoted as 1k, 0.2 mmol, 45.0 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product was collected. The trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) was placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 9:1) to give a diboronate ester aromatic compound with the structure shown in 3k (white solid, 2,2'-(4-(trifluoromethyl)-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in a yield of 23%.

[0087] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.90 (s, 1H), 7.73 (d, J = 7.8Hz, 1H), 7.63-7.60 (m, 1H), 1.38 (d, J = 1.2Hz, 24H). 13 C NMR (101MHz, CDCl3) δ 133.5, 130.9 (q, J = 32.3MHz), 130.0 (q, J = 3.7MHz), 125.7 (q, J = 3.9MHz), 124.3 (q, J = 273.7MHz), 84.4, 84.3, 24.9. 11 B NMR(128MHz,CDCl3)δ31.22.HRMS(ESI)m / z:[M+Na] + Calcd forC 19 H 27 B2O4F3Na + 421.1940; Found 421.1942.

[0088] Example 12

[0089]

[0090] In a nitrogen-filled glove box, p-bromotrifluoromethoxybenzene (denoted as 1 L, 0.2 mmol, 48.2 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product was collected. The trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) was placed in acetonitrile (2 mL) and reacted for 1 h. Then, the mixture was purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 4:1) to give a diboronate ester aromatic compound with the structure shown in 3l (white solid, 2,2'-(4-(trifluoromethoxy)-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in 35% yield.

[0091] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.69 (d, J = 8.2Hz, 1H), 7.45 (s, 1H), 7.24-7.19 (m, 1H), 1.36 (s, 24H). 13 C NMR (101MHz, CDCl3) δ150.3, 135.5, 125.5, 121.3, 120.5 (q, J = 258.2MHz), 84.3, 84.2, 24.9. 11 B NMR(128MHz,CDCl3)δ31.32.HRMS(ESI)m / z:[M+Na] + Calcd for C 19 H 27 B2O5F3Na + 437.1889; Found 437.1892.

[0092] Example 13

[0093]

[0094] In a nitrogen-filled glove box, p-bromotrifluoromethylthiobenzene (denoted as 1m, 0.2 mmol, 51.4 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product and trimethyl methyl ether were then separated. Methylamine N-oxide dihydrate (0.9 mmol, 100 mg) was placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether:ethyl acetate, v / v = 9:1) to give a diboronate aromatic compound (white solid, 2,2'-(4-((trifluoromethyl)thio)-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) with the structure shown in 3m, in 38% yield. Product characterization data are as follows: 1 HNMR (400MHz, CDCl3) δ7.91(s,1H),7.80(s,1H),7.67(s,1H),1.37(s,24H). 13 C NMR (101MHz, CDCl3) δ140.9, 136.6, 134.3, 133.9, 126.8 (q, J = 258.3MHz), 84.4, 83.9, 24.9. 11 B NMR(128MHz,CDCl3)δ31.00.HRMS(ESI)m / z:[M+Na] + Calcd for C 19 H 27 B2O4SF3Na + 453.1660; Found 453.1664.

[0095] Example 14

[0096]

[0097] In a nitrogen-filled glove box, 1-bromo-4-trimethylsilylbenzene (denoted as 1n, 0.2 mmol, 45.8 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed. The crude product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. Then, the mixture was purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound with the structure shown in 3n (white solid, (3,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaboron-2-yl)phenyl)trimethylsilane) in a yield of 57%.

[0098] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.76(s,1H),7.62(d,J=7.3Hz,1H),7.52(dd,J=7.3,1.1Hz,1H),1.37(s,12H),1.35(s,12H),0.24(s,9H). 13 CNMR (101MHz, CDCl3) δ142.5,139.1,135.2,133.7,84.9,84.98,26.1,26.0,-0.00. 11 B NMR(128MHz,CDCl3)δ31.90.HRMS(ESI)m / z:[M+Na] + Calcd for C 24 H 42 B2O5SiNa + 425.2461; Found 425.2461.

[0099] Example 15

[0100]

[0101] In a nitrogen-filled glove box, (4-bromophenoxy)-tert-butyldimethylsilane (denoted as 1o, 0.2 mmol, 57.5 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. The mixture was stirred at 40 °C for 24 h, after which the solvent was completely removed. The crude product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. Then, the mixture was purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound with the structure shown in 3o (white solid, (3,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxoboron-2-yl)phenoxy)(tert-butyl)dimethylsilane), in a yield of 63%).

[0102] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.42(d,J=8.1Hz,1H),6.89(d,J=2.4Hz,1H),6.66(dd,J=8.1,2.5Hz,1H),1.20(s,12H),1.17(s,12H),0.80(s,9H),-0.00(s,6H). 13 C NMR (101MHz, CDCl3) δ156.9,135.9,124.9,120.6,83.9,83.7,25.7,24.9,18.2,-4.4. 11 B NMR(128MHz,CDCl3)δ31.53.HRMS(ESI)m / z:[M+Na] + Calcd forC 24 H 42 B2O5SiNa + 483.2880; Found 483.2881.

[0103] Example 16

[0104]

[0105] In a nitrogen-filled glove box, 4-bromophenylboronic acid pinacol ester (denoted as 1p, 0.2 mmol, 56.6 mg), pinacol diboronic acid ester (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude... The product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 5:1) to give a diboronate ester aromatic compound with the structure shown at 3p (white solid, 2,2',2”-(benzene-1,2,4-triyl)tris(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in 64% yield.

[0106] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ8.08 (s, 1H), 7.82-7.78 (m, 1H), 7.64-7.60 (m, 1H), 1.36 (d, J = 1.1Hz, 24H), 1.34 (s, 12H). 13 C NMR (101MHz, CDCl3) δ139.6,135.4,132.5,83.9,83.8,83.7,25.0,24.9,24.8. 11 B NMR(128MHz,CDCl3)δ31.70.HRMS(ESI)m / z:[M+Na] + Calcd for C 24 H 39 B3O6Na + 479.2918; Found 479.2921.

[0107] Example 17

[0108]

[0109] In a nitrogen-filled glove box, 2-bromotoluene (denoted as 1q, 0.2 mmol, 34.2 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product was collected. The trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) was placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound with the structure shown in 3q (white solid, 2,2'-(3-methyl-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in a yield of 67%.

[0110] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.68-7.57(m,1H),7.27-7.17(m,2H),2.41(s,3H),1.43(s,12H),1.33(s,12H). 13 C NMR (101MHz, CDCl3) δ140.4,132.2,131.7,128.1,83.8,25.5,24.9,21.9. 11 B NMR(128MHz,CDCl3)δ31.31.HRMS(ESI)m / z:[M+Na] + Calcd for C 19 H 30 B2O4Na + 367.2222; Found 367.2225.

[0111] Example 18

[0112]

[0113] In a nitrogen-filled glove box, 2-bromoethylbenzene (denoted as 1r, 0.2 mmol, 37.0 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product was collected. The trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) was placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound (white solid, 2,2'-(3-ethyl-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) with the structure shown in 3r, in a yield of 57%.

[0114] The product characterization data are as follows: 1 HNMR (400MHz, CDCl3) δ7.65(dd,J=6.9,1.6Hz,1H),7.30-7.22(m,2H),2.70(q,J=7.6Hz,2H),1.44(s,12H),1.33(s,12H),1.22(t,J=7.6Hz,3H). 13 C NMR (101MHz, CDCl3) δ147.1,132.5,130.4,128.2,83.9,83.8,29.3,25.5,24.9,16.8. 11 B NMR(128MHz,CDCl3)δ31.43.HRMS(ESI)m / z:[M+Na] + Calcd for C 20 H 32 B2O4Na + 381.2379; Found 381.2380.

[0115] Example 19

[0116]

[0117] In a nitrogen-filled glove box, 1-bromo-2-isopropylbenzene (denoted as 1s, 0.2 mmol, 39.8 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude... The product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound with the structure shown in 3S (white solid, 2,2'-(3-isopropyl-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in 60% yield.

[0118] The product characterization data are as follows: 1 HNMR (400MHz, CDCl3) δ7.66(dd,J=7.1,1.3Hz,1H),7.36-7.28(m,2H),3.07(hept,J=6.7Hz,1H),1.44(s,12H),1.33(s,12H),1.25(d,J=6.2Hz,6H). 13 CNMR (101MHz, CDCl3) δ151.5,132.9,128.3,126.9,83.9,83.8,33.6,29.7,25.6,24.8,24.4. 11 B NMR(128MHz,CDCl3)δ31.89.HRMS(ESI)m / z:[M+Na] + Calcd for C 21 H 34 B2O4Na + 395.2535; Found 395.2539.

[0119] Example 20

[0120]

[0121] In a nitrogen-filled glove box, 1-bromo-3-(methoxymethyl)benzene (denoted as 1t, 0.2 mmol, 40.2 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed. The crude product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 8:1) to give a diboronate ester aromatic compound with the structure shown in 3t (white solid, 2,2'-(3-(methoxymethyl)-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in 42% yield.

[0122] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.74(d,J=7.2Hz,1H),7.38(d,J=7.2Hz,1H),7.31(t,J=7.5Hz,1H),4.55(s,2H),3.29(s,3H),1.44(s,12H),1.34(s,12H). 13 C NMR (101MHz, CDCl3) δ141.3,134.4,130.2,128.1,84.0,83.9,74.5,57.4,25.5,24.9. 11 B NMR(128MHz,CDCl3)δ31.89.HRMS(ESI)m / z:[M+Na] + Calcd for C 20 H 32 B2O5Na + 397.2328; Found 397.2324.

[0123] Example 21

[0124]

[0125] In a nitrogen-filled glove box, 2,3-dimethylbromobenzene (denoted as 1u, 0.2mmol, 37.0mg), pinacol diborate (denoted as 2a, 0.6mmol, 152.4mg), titanium catalyst (10mol%, 6.9mg), and lithium tert-butoxide (0.3mmol, 24mg) were placed in 1mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40°C for 24 hours, the solvent was completely removed, and the crude product was... The compound and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound (white solid, 2,2'-(3,4-dimethyl-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) with the structure shown in Figure 3, in a yield of 62%.

[0126] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.57(d,J=7.5Hz,1H),7.10(d,J=7.5Hz,1H),2.31(s,3H),2.24(s,3H),1.44(s,12H),1.32(s,12H). 13 C NMR (101MHz, CDCl3) δ138.9,138.6,132.9,129.7,83.8,83.7,25.6,24.8,20.6,18.9. 11 BNMR(128MHz,CDCl3)δ31.23.HRMS(ESI)m / z:[M+Na] + Calcd for C 20 H 32 B2O4Na + 381.2379; Found 381.2381.

[0127] Example 22

[0128]

[0129] In a nitrogen-filled glove box, 4-bromo-2,6-dimethyl anisole (denoted as 1v, 0.2 mmol, 43.0 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product was... The compound and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 9:1) to give a diboronate ester aromatic compound with the structure shown in 3v (white solid, 2,2'-(4-methoxy-3,5-dimethyl-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in 62% yield.

[0130] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.50(s,1H),3.66(s,3H),2.34(s,3H),2.25(s,3H),1.43(s,12H),1.32(s,12H). 13 C NMR (101MHz, CDCl3) δ158.9,136.4,133.3,130.5,83.8,83.7,59.6,25.5,24.8,15.9,15.0. 11 B NMR(128MHz,CDCl3)δ31.88.HRMS(ESI)m / z:[M+Na] + Calcd for C 21 H 34 B2O5Na + 411.2485; Found 411.2487.

[0131] Example 23

[0132]

[0133] In a nitrogen-filled glove box, 2-bromonaphthalene or 1-bromonaphthalene (denoted as 1w, 0.2 mmol, 41.4 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product and trimethylamine N-oxide were collected. The dihydrate (0.9 mmol, 100 mg) was placed in acetonitrile (2 mL) and reacted for 1 h. Then, it was purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound (white solid, 2,2'-(naphthalene-1,2-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxoborane)) with the structure shown in Figure 3w. The yield was 36% when using 2-bromonaphthalene as the starting material and 42% when using 1-bromonaphthalene as the starting material.

[0134] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ8.11(dt,J=6.2,3.2Hz,1H),7.85-7.78(m,3H),7.47(dt,J=6.3,3.4Hz,2H),1.52(s,12H),1.39(s,12H). 13 CNMR(101MHz, CDCl3)δ135.7,134.1,130.5,128.3,128.2,128.1,126.3,125.7,84.3,84.1,25.5,24.9. 11 B NMR(128MHz,CDCl3)δ31.11.HRMS(ESI)m / z:[M+Na] + Calcd for C 22 H 30 B2O4Na + 403.2222; Found 403.2225.

[0135] Example 24

[0136]

[0137] In a nitrogen-filled glove box, 6-bromo-1,2,3,4-tetrahydronaphthalene (denoted as 1x, 0.2 mmol, 42.2 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude... The product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound with the structure shown in 3x (white solid, 2,2'-(5,6,7,8-tetrahydronaphthalene-1,2-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in 43% yield.

[0138] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.54(d,J=7.6Hz,1H),7.02(d,J=7.6Hz,1H),2.84(t,J=6.2Hz,2H ),2.74(t,J=6.1Hz,2H),1.76(dp,J=16.7,6.0,5.5Hz,4H),1.43(s,12H),1.32(s,12H). 13 C NMR (101MHz, CDCl3) δ139.3,132.3,129.2,83.7,83.6,30.3,29.1,25.5,24.8,23.6,22.8. 11 B NMR(128MHz,CDCl3)δ31.98.HRMS(ESI)m / z:[M+Na] + Calcd for C 22 H 34 B2O4Na + 407.2535; Found 407.2537.

[0139] Example 25

[0140]

[0141] In a nitrogen-filled glove box, 6-bromo-1,4-benzoxane (denoted as 1y, 0.2 mmol, 43.0 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product and trimethylolpropionate were collected. Amine N-oxide dihydrate (0.9 mmol, 100 mg) was placed in acetonitrile (2 mL) and reacted for 1 h. Then, it was purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 5:1) to give a diboronate ester aromatic compound with the structure shown in 3y (white solid, 2,2'-(2,3-dihydrobenzo[b][1,4]dioxin-5,6-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in 57% yield.

[0142] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.32(d,J=8.0Hz,1H),6.81(d,J=8.0Hz,1H),4.24(q,J=4.9Hz,4H),1.41(s,12H),1.30(s,12H). 13 C NMR (101MHz, CDCl3) δ145.9,145.3,129.4,117.3,83.9,83.7,64.4,64.1,25.1,24.8. 11 BNMR(128MHz,CDCl3)δ31.55.HRMS(ESI)m / z:[M+Na] + Calcd for C 20 H 30 B2O6Na + 411.2121; Found 411.2122.

[0143] Example 26

[0144]

[0145] In a nitrogen-filled glove box, 4-bromo-1,2-methylenedioxybenzene (denoted as 1z, 0.2 mmol, 40.2 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. The mixture was stirred at 40 °C for 24 h, after which the solvent was completely removed. The crude product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 6:1) to give a diboronate ester aromatic compound (white solid, 5,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxoboron-2-yl)benzo[d][1,3]dioxazole) with the structure shown in 3z, in a yield of 42%.

[0146] The product characterization data are as follows: 1 HNMR (400MHz, CDCl3) δ7.12(s,2H),5.92(s,2H),1.35(s,24H). 13 C NMR (101MHz, CDCl3) δ148.6,113.6,100.6,83.9,24.9. 11 B NMR(128MHz,CDCl3)δ31.37.HRMS(ESI)m / z:[M+Na] + Calcd for C 19 H 28 B2O6Na + 397.1964; Found 397.1965.

[0147] Example 27

[0148]

[0149] In a nitrogen-filled glove box, 5-bromo-1-methyl-1H-indole (denoted as 1aa, 0.2 mmol, 42.0 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed. The crude product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. Then, the mixture was purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 4:1) to give a diboronate ester aromatic compound with the structure shown in 3aa (white solid, 1-methyl-4,5-bis(4,4,5,5-tetramethyl-1,3,2-dioxoboronan-2-yl)-1H-indole) in a yield of 41%.

[0150] The product characterization data are as follows: 1 H NMR(400MHz, CDCl3) δ7.62(d,J=8.3Hz,1H),7.30(dd,J=8.3,0.7Hz,1H),7.03(d,J =3.1Hz,1H),6.67(dd,J=3.1,0.7Hz,1H),3.76(s,3H),1.45(s,12H),1.36(s,12H). 13 C NMR (101MHz, CDCl3) δ137.2,132.2,128.7,127.7,109.4,102.5,83.7,83.5,32.7,25.2,24.9. 11 B NMR(128MHz,CDCl3)δ32.31.HRMS(ESI)m / z:[M+Na] + Calcdfor C 21 H 31 B2NO4Na + 406.2331; Found 406.2331.

[0151] Example 28

[0152]

[0153] In a nitrogen-filled glove box, 1-(4-bromophenyl)pyrrole (denoted as 1ab, 0.2 mmol, 45.2 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. The mixture was stirred at 40 °C for 24 h, after which the solvent was completely removed. The crude product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 4:1) to give a diboronate ester aromatic compound (white solid, 1-(3,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxoboron-2-yl)phenyl)-1H-pyrrole) with the structure shown in 3ab, in a yield of 52%.

[0154] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.73 (s, 1H), 7.64 (d, J = 2.2Hz, 1H), 7.41-7.38 (m, 1H), 7.14 (t, J = 2.2Hz, 2H), 6.33 (t, J = 2.1Hz, 2H), 1.38 (d, J = 5.5Hz, 24H). 13 C NMR (101MHz, CDCl3) δ135.4,124.9,120.8,119.3,110.4,84.2,84.0,25.0,24.9. 11 BNMR(128MHz,CDCl3)δ31.88.HRMS(ESI)m / z:[M+Na] + Calcd for C 22 H 31 B2NO4Na + 418.2331; Found 418.2335.

[0155] Example 29

[0156]

[0157] In a nitrogen-filled glove box, m-bromoanisole (denoted as 1ac, 0.2 mmol, 37.4 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product was collected. The trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) was placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 9:1) to give a diboronate ester aromatic compound with the structure shown in 3ac (white solid, 2,2'-(3-methoxy-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in a yield of 57%.

[0158] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.73 (s, 1H), 7.64 (d, J = 2.2Hz, 1H), 7.41-7.38 (m, 1H), 7.14 (t, J = 2.2Hz, 2H), 6.33 (t, J = 2.1Hz, 2H), 1.38 (d, J = 5.5Hz, 24H). 13 C NMR (101MHz, CDCl3) δ135.4,124.9,120.8,119.3,110.4,84.2,84.0,25.0,24.9. 11 BNMR(128MHz,CDCl3)δ31.88.HRMS(ESI)m / z:[M+Na] + Calcd for C 22 H 31 B2NO4Na + 418.2331; Found 418.2335.

[0159] Example 30

[0160]

[0161] In a nitrogen-filled glove box, 2-bromo-1,3,5-trimethylbenzene (denoted as 1ad, 0.2 mmol, 39.8 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. The mixture was stirred at 40 °C for 24 h, after which the solvent was completely removed. The crude product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 9:1) to give a diboronate ester aromatic compound with the structure shown in 3ad (white solid, 2,2'-(2,4,6-trimethyl-1,3-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in 42% yield.

[0162] The product characterization data are as follows: 1 HNMR (400MHz, CDCl3) δ6.73(s,1H),2.44(s,3H),2.31(s,6H),1.36(s,24H). 13 C NMR (101MHz, CDCl3) δ145.5,142.6,127.5,83.4,24.9,22.5,22.2. 11 B NMR(128MHz,CDCl3)δ31.99.HRMS(ESI)m / z:[M+Na] + Calcd for C 21 H 34 B2O4Na + 395.2535; Found 395.2533.

[0163] Example 31

[0164]

[0165] In a nitrogen-filled glove box, 1-bromo-2,3,5,6-tetramethylbenzene (denoted as 1ae, 0.2 mmol, 42.6 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. The mixture was stirred at 40 °C for 24 h, after which the solvent was completely removed. The crude product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 9:1) to give a diboronate ester aromatic compound with the structure shown in 3ae (white solid, 2,2'-(2,3,5,6-tetramethyl-1,4-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in 24% yield.

[0166] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ2.21 (s, 12H), 1.39 (s, 24H). 13 C NMR (101MHz, CDCl3) δ135.8,83.6,25.1,19.4. 11 B NMR(128MHz,CDCl3)δ32.96.HRMS(ESI)m / z:[M+Na] + Calcd for C 22 H 36 B2O4Na + 409.2692; Found 409.2698.

[0167] Example 32

[0168]

[0169] In a nitrogen-filled glove box, 4-iodotoluene (denoted as 1af, 0.2 mmol, 43.6 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. The mixture was stirred at 40 °C for 24 h, after which the solvent was completely removed, and the crude product was... The compound and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound (white solid, 2,2'-(4-methyl-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) with the structure shown in 3a, in a yield of 63%.

[0170] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.57(d,J=7.6Hz,1H),7.45(s,1H),7.20-7.16(m,1H),2.32(s,3H),1.37(s,12H),1.35(s,12H). 13 C NMR (101MHz, CDCl3) δ138.9,134.1,133.9,129.8,83.8,83.7,24.92,24.90,21.5. 11 BNMR(128MHz,CDCl3)δ31.40.HRMS(ESI)m / z:[M+Na] + Calcd for C 19 H 30 B2O4Na + 367.2222; Found 367.2227.

[0171] Example 33

[0172]

[0173] In a nitrogen-filled glove box, 4-iodoanisidine (1 ag, 0.2 mmol, 50.0 mg), pinacol diborate (2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. The mixture was stirred at 40 °C for 24 h, after which the solvent was completely removed, and the crude product was... The compound and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. Then, the mixture was purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 9:1) to give a diboronate ester aromatic compound (white solid, 2,2'-(4-(methylthio)-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) with the structure shown in 3f, in a yield of 51%.

[0174] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.60(d,J=7.9Hz,1H),7.48(d,J=1.7Hz,1H),7.24(dd,J=7.9,2.0Hz,1H),2.47(s,3H),1.35(s,24H). 13 CNMR (101MHz, CDCl3) δ140.3,134.3,130.9,126.6,84.0,83.8,24.9,24.8,15.4.

[0175] 11 B NMR(128MHz,CDCl3)δ31.57.HRMS(ESI)m / z:[M+Na] + Calcd for C 19 H 30 B2O4SNa + 399.1943; Found 399.1945.

[0176] Example 34

[0177]

[0178] In a nitrogen-filled glove box, 1-iodo-3,4-methylenedioxybenzene (denoted as 1ah, 0.2 mmol, 49.6 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed. The crude product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 6:1) to give a diboronate ester aromatic compound (white solid, 5,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxoboron-2-yl)benzo[d][1,3]dioxazole) with the structure shown in 3z, in a yield of 42%.

[0179] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.12(s,2H),5.92(s,2H),1.35(s,24H). 13 C NMR (101MHz, CDCl3) δ148.6,113.6,100.6,83.9,24.9. 11 B NMR(128MHz,CDCl3)δ31.37.HRMS(ESI)m / z:[M+Na] + Calcd for C 19 H 28 B2O6Na + 397.1964; Found 397.1965.

[0180] Example 35

[0181]

[0182] In a nitrogen-filled glove box, 4-(4-iodophenyl)morpholine (denoted as 1ai, 0.2 mmol, 57.8 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed. The crude product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. Then, column chromatography was performed to purify the product (eluent: petroleum ether: ethyl acetate, volume ratio = 2:1) to give a diboronate ester aromatic compound (white solid, 4-(3,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxoboron-2-yl)phenyl)morpholine) with the structure shown in 3ai, in a yield of 56%.

[0183] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.63(d,J=8.3Hz,1H),7.11(d,J=2.3Hz,1H),6.89(s,1H),3.89-3.79(m,4H),3.25-3.15(m,4H),1.37(s,12H),1.33(s,12H). 13 C NMR (101MHz, CDCl3) δ135.7,119.7,115.6,83.8,83.5,66.9,48.7,29.7,24.9,24.8. 11 BNMR(128MHz,CDCl3)δ31.82.HRMS(ESI)m / z:[M+Na] + Calcd for C 22 H 35 B2NO5Na + 438.2594; Found 438.2598.

[0184] Example 36

[0185]

[0186] In a nitrogen-filled glove box, 1-tert-butyl-4-iodobenzene (denoted as 1aj, 0.2 mmol, 52.0 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product was... The compound and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound with the structure shown in 3aj (white solid, 2,2'-(4-(tert-butyl)-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in a yield of 66%.

[0187] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δδ7.65-7.57(m,2H),7.40(dd,J=7.9,2.1Hz,1H),1.37(s,12H),1.34(s,12H),1.30(s,9H). 13 C NMR (101MHz, CDCl3) δ151.9,133.7,129.9,126.1,83.7,83.6,34.7,31.2,25.0,24.9. 11 B NMR(128MHz,CDCl3)δ31.32.HRMS(ESI)m / z:[M+Na] + Calcd for C 22 H 36 B2O4Na + 409.2692; Found 409.2694.

[0188] Example 37

[0189]

[0190] In a nitrogen-filled glove box, 4-chloroanisole (denoted as 1ak, 0.2 mmol, 28.5 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product was... The compound and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 9:1) to give a diboronate ester aromatic compound with the structure shown in 3e (white solid, 2,2'-(4-methoxy-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in a yield of 56%.

[0191] The product characterization data are as follows: 1 HNMR (400MHz, CDCl3) δ7.66(d,J=8.3Hz,1H),7.11(d,J=2.6Hz,1H),6.89(dd,J=8.3,2.6Hz,1H),3.82(s,3H),1.38(s,12H),1.34(s,12H). 13 C NMR (101MHz, CDCl3) δ160.6,136.1,118.2,114.6,83.9,83.7,55.1,29.7,24.9,24.8. 11 B NMR(128MHz,CDCl3)δ31.06.HRMS(ESI)m / z:[M+Na] + Calcd for C 19 H 30 B2O5Na + 383.2172; Found 383.2172.

[0192] Example 38

[0193]

[0194] In a nitrogen-filled glove box, 3-chloro-o-xylene (denoted as 1a, 0.2 mmol, 28.1 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product was... The compound and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound (white solid, 2,2'-(3,4-dimethyl-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) with the structure shown in Figure 3, in a yield of 62%.

[0195] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.57(d,J=7.5Hz,1H),7.10(d,J=7.5Hz,1H),2.31(s,3H),2.24(s,3H),1.44(s,12H),1.32(s,12H). 13 C NMR (101MHz, CDCl3) δ138.9,138.6,132.9,129.7,83.8,83.7,25.6,24.8,20.6,18.9. 11 BNMR(128MHz,CDCl3)δ31.23.HRMS(ESI)m / z:[M+Na] + Calcd for C 20 H 32 B2O4Na + 381.2379; Found 381.2381.

[0196] Example 39

[0197]

[0198] In a nitrogen-filled glove box, 2-chloro-6-fluorotoluene (denoted as 1am, 0.2 mmol, 28.9 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product was collected. The trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) was placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound (white solid, 2,2'-(4-fluoro-3-methyl-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) with the structure shown in 3am, in a yield of 38%.

[0199] The product characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ7.64(dd,J=8.1,5.7Hz,1H),6.96(dd,J=10.0,8.3Hz,1H),2.32(d,J=2.2Hz,3H),1.44(s,12H),1.32(s,12H). 13 C NMR (101MHz, CDCl3) δ162.9 (d, J = 250.2Hz), 135.0 (d, J = 8.3Hz), 127.1 (d, J = 14 .6Hz), 114.8 (d, J = 21.9Hz), 84.1 (d, J = 18.4Hz), 25.5, 24.8, 13.5 (d, J = 5.1Hz). 11 B NMR(128MHz,CDCl3)δ31.10.HRMS(ESI)m / z:[M+Na] + Calcd for C 19 H 29 B2FO4Na + 385.2128; Found 385.2134.

[0200] Example 40

[0201]

[0202] In a nitrogen-filled glove box, 3,5-dimethylchlorobenzene (denoted as 1an, 0.2 mmol, 28.1 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. The mixture was stirred at 40 °C for 24 h, after which the solvent was completely removed, and the crude product was... The compound and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound (white solid, 2,2'-(3,5-dimethyl-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) with the structure shown in 3an, in a yield of 34%.

[0203] The product characterization data are as follows: 1 HNMR (400MHz, CDCl3) δ7.43(s,1H),7.02(s,1H),2.38(s,3H),2.27(s,3H),1.42(s,12H),1.33(s,12H). 13 C NMR (101MHz, CDCl3) δ140.6,137.6,132.8,132.6,83.8,83.7,25.4,24.9,21.8,21.2. 11 B NMR(128MHz,CDCl3)δ31.69.HRMS(ESI)m / z:[M+Na] + Calcd for C 20 H 32 B2O4Na + 381.2379; Found 381.2378.

[0204] Example 41

[0205]

[0206] In a nitrogen-filled glove box, 2-chloro-1,4-dimethylbenzene (denoted as 1ao, 0.2 mmol, 28.1 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude... The product and trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) were placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound with the structure shown in 3ao (white solid, 2,2'-(3,6-dimethyl-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in a yield of 39%.

[0207] The product characterization data are as follows: 1 HNMR(400MHz, CDCl3)δ7.03(s,2H),2.41(s,6H),1.38(s,24H). 13 C NMR (101MHz, CDCl3) δ130.9,83.7,25.2,22.1. 11 B NMR(128MHz,CDCl3)δ31.67.HRMS(ESI)m / z:[M+Na] + Calcd for C 20 H 32 B2O4Na + 381.2379; Found 381.2380.

[0208] Example 42

[0209]

[0210] In a nitrogen-filled glove box, 4-tert-butylchlorobenzene (denoted as 1ap, 0.2 mmol, 33.7 mg), pinacol diborate (denoted as 2a, 0.6 mmol, 152.4 mg), titanium catalyst (10 mol%, 6.9 mg), and lithium tert-butoxide (0.3 mmol, 24 mg) were placed in 1 mL of methyl tert-butyl ether and mixed in a pressure-resistant tube with a magnetic stir bar. After stirring at 40 °C for 24 h, the solvent was completely removed, and the crude product was collected. The trimethylamine N-oxide dihydrate (0.9 mmol, 100 mg) was placed in acetonitrile (2 mL) and reacted for 1 h. The mixture was then purified by column chromatography (eluent: petroleum ether: ethyl acetate, volume ratio = 10:1) to give a diboronate ester aromatic compound with the structure shown in 3aj (white solid, 2,2'-(4-(tert-butyl)-1,2-phenyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane)) in a yield of 66%.

[0211] The product characterization data are as follows: 1 HNMR (400MHz, CDCl3) δ 7.65-7.57 (m, 2H), 7.40 (dd, J = 7.9, 2.1Hz, 1H), 1.37 (s, 12H), 1.34 (s, 12H), 1.30 (s, 9H). 13 C NMR (101MHz, CDCl3) δ151.9,133.7,129.9,126.1,83.7,83.6,34.7,31.2,25.0,24.9. 11 B NMR(128MHz,CDCl3)δ31.32.HRMS(ESI)m / z:[M+Na] + Calcd for C 22 H 36 B2O4Na + 409.2692; Found 409.2694.

[0212] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a diboron ester-based aromatic compound, comprising the following steps: Under a protective atmosphere, aryl halides, pinacol diboronic acid esters, titanium catalysts, basic reagents, and solvents are mixed and subjected to a substitution reaction to obtain diboronic acid ester aromatic compounds.

2. The preparation method according to claim 1, characterized in that, The molar ratio of the aryl halide to pinacol diboronic acid ester is 1:2 to 5.

3. The preparation method according to claim 1 or 2, characterized in that, The aryl group in the aryl halogen includes indolyl, pyrroleyl, tetrahydronaphthyl, benzodioxane, piperonyl, naphthyl, phenyl, substituted phenyl or substituted naphthyl; the halogen in the aryl halogen includes one or more of fluorine, chlorine, bromine and iodine.

4. The preparation method according to claim 3, characterized in that, The substituents in the substituted phenyl and substituted naphthyl groups independently include one or more of the following: halogen, C1-C4 alkyl, phenyl, benzyl, methoxy, benzylmethoxy, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methylthio, N,N-dimethyl, trimethylsilyl, tert-butyldimethylsiloxy, pinacol boronic acid ester, methyloxymethyl, pyrrolyl, and morpholinyl.

5. The preparation method according to claim 1, characterized in that, The molar ratio of the aryl halide to the titanium catalyst is 1:0.025 to 0.

2.

6. The preparation method according to claim 1 or 5, characterized in that, The titanium catalyst comprises titanium complexes.

7. The preparation method according to claim 6, characterized in that, The titanium complex comprises titanium dichlorodicyclopentadiene and / or Rosenthal Ti, wherein the structural formula of Rosenthal Ti is as follows:

8. The preparation method according to claim 1, characterized in that, The alkaline reagent includes metal alkoxides and / or carbonates; The molar ratio of the aryl halide to the basic reagent is 1:0.25 to 2.

9. The preparation method according to claim 1, characterized in that, The solvents include ether solvents and / or benzene solvents.

10. The preparation method according to any one of claims 1-2, 4-5 and 7-9, characterized in that, The substitution reaction is carried out at a temperature of 25–120°C for a time of 15–30 h.

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