CN112645971B

CN112645971B - Method for directly preparing alkyl borate compound from alkyl halide

Info

Publication number: CN112645971B
Application number: CN202110073552.5A
Authority: CN
Inventors: 吴立朋; 王先津
Original assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Current assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Priority date: 2021-01-20
Filing date: 2021-01-20
Publication date: 2021-12-24
Anticipated expiration: 2041-01-20
Also published as: CN112645971A

Abstract

The invention relates to a method for directly preparing alkyl borate compounds from alkyl halides, which comprises the following steps: in a protective atmosphere, mixing a titanium metal catalyst, an alkali compound, a borate compound and an alkyl halide or sulfonate compound, and reacting at 35-100 ℃ for 8-24 hours, namely directly converting the alkyl halide or sulfonate compound into an alkyl boronic acid pinacol ester compound. The method has the advantages of simple operation, low cost, good functional group tolerance and wide substrate application range.

Description

Method for directly preparing alkyl borate compound from alkyl halide

Technical Field

The invention relates to the technical field of organic synthesis, in particular to a method for directly preparing alkyl borate compounds from alkyl halides.

Background

The alkyl borate compounds are important organic synthesis intermediates, can be cross-coupled with an electrophilic reagent to prepare drug molecules, and play an important role in pharmaceutical chemistry application. Alkyl borate compounds are traditionally prepared by using metal reagents such as alkyl lithium, alkyl magnesium and the like through transmetallization reaction, but the application range of substrates is narrow. In addition, olefin hydroboration reaction can also be used for preparing alkyl borate compounds, but due to multiple reaction sites of olefin and occurrence of olefin isomerization, selectivity of the olefin is very challenging.

In recent years, scientists have focused on the use of boronation of alkyl halides as an alternative method for preparing alkyl borate esters, which has the advantages of using abundant or readily available alkyl halides as starting materials, reducing synthesis costs, and avoiding regioselectivity problems in the olefin hydroboration reaction. Scientists have developed processes for the conversion of alkyl halides to alkyl borate compounds based on transition metal catalysts such as Cu, Ni, Pd, Rh, Zn, Fe, Mn, etc. However, B is used in all of these known methods₂pin₂Or B₂cat₂As a boronizing agent, no report has been found on the study of HBpin or HBcat as a boron source.

Disclosure of Invention

The invention aims to solve the technical problem of providing a method for directly preparing alkyl borate compounds from alkyl halides, which has the advantages of simple operation, low cost, good functional group tolerance and wide substrate application range.

In order to solve the problems, the method for directly preparing the alkyl borate compound by using the alkyl halide is characterized by comprising the following steps of: in a protective atmosphere, mixing a titanium metal catalyst, an alkali compound, a borate compound and an alkyl halide or sulfonate compound, and reacting at 35-100 ℃ for 8-24 hours, namely directly converting the alkyl halide or sulfonate compound into an alkyl boronic acid pinacol ester compound; the molar ratio of the alkyl halide or sulfonate compound, the titanium metal catalyst, the alkali compound and the borate compound is 1: 0.05-0.1: 0.25-1: 2 to 3.

The reaction equation is as follows:

an organic solvent is also added in the mixing process of the titanium metal catalyst, the alkali compound, the borate compound and the alkyl halide or sulfonate compound; the molar ratio of the alkyl halide or sulfonate compound to the organic solvent is 0.2 mmol: 1 mL.

The structural formula of the alkyl halide or sulfonate compound is as follows:

(ii) a In the formula: r¹Is one of benzyl, substituted benzyl, heterocycle, substituted heterocycle, alkyl or alkenyl; r²And R³Are both alkyl or hydrogen.

The R is¹Is one of benzyl, substituted benzyl, heterocycle, substituted heterocycle, alkyl or alkenyl.

And the substituent in the substituted benzyl is one of methyl, methoxy, ester, fluorine, chlorine, bromine, phenyl or trifluoromethyl.

The titanium metal catalyst is one of bis (cyclopentadienyl) titanium dichloride, (cyclopentadienyl) titanium trichloride, bis (tert-butylcyclopentadienyl) titanium dichloride, pentamethylcyclopentadienyl titanium trichloride and bis (pentamethylcyclopentadienyl) titanium dichloride.

The borate compound is pinacol borane or naphthol borane.

The alkali compound is one of potassium methoxide, sodium methoxide, lithium methoxide, potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, cesium carbonate, cesium fluoride, silver acetate, lithium carbonate, lithium hydride and methyllithium.

The organic solvent is one of N-hexane, dioxane, chloroform, N-dimethylformamide, ethyl acetate, diethylene glycol dimethyl ether, methyl tert-butyl ether, tetrahydrofuran, dichloromethane, acetonitrile and toluene.

The protective atmosphere refers to nitrogen atmosphere or argon atmosphere, and the pressure is 1 atm.

Compared with the prior art, the invention has the following advantages:

1. the method uses the titanium metal which is relatively cheap and widely exists in the nature, and reduces the reaction cost.

2. The method takes titanium metal as a catalyst, takes HBpin or HBcat as a boron source, can directly convert alkyl halide or sulfonate compound into the alkyl boronic acid pinacol ester compound, and has the advantages of simple operation, low cost, good functional group tolerance and wide substrate application range. Meanwhile, the reaction that the alkyl halide reacts with the borane to generate saturated alkane through hydrogenation dehalogenation reaction, which is often generated by using other transition metal catalysts, is avoided.

3. The synthesized borate compound has high yield and good selectivity, and is beneficial to separation and purification of products.

Detailed Description

A method for directly preparing alkyl borate compounds from alkyl halides comprises the following steps: in a nitrogen or argon protective atmosphere with the pressure of 1atm, mixing a titanium metal catalyst, an alkaline compound, a borate compound and an alkyl halide or sulfonate compound, and reacting for 8-24 hours at 35-100 ℃, namely directly converting the alkyl halide or sulfonate compound into an alkyl boronic acid pinacol ester compound.

Wherein: the molar ratio of the alkyl halide or sulfonate compound to the titanium metal catalyst to the alkali compound to the borate compound is 1: 0.05-0.1: 0.25-1: 2 to 3.

An organic solvent is also added in the mixing process of the titanium metal catalyst, the alkali compound, the borate compound and the alkyl halide or sulfonate compound; the volume ratio of the molar weight of the alkyl halide or sulfonate compound to the organic solvent is 0.2 mmol: 1 mL.

The structural formula of the alkyl halide or sulfonate compound is as follows:

(ii) a In the formula: r¹Is one of benzyl, substituted benzyl, heterocycle, substituted heterocycle, alkyl or alkenyl; r²And R³Are both alkyl or hydrogen. R¹Is one of benzyl, substituted benzyl, heterocycle, substituted heterocycle, alkyl or alkenyl. The substituent in the substituted benzyl is one of methyl, methoxy, ester, fluorine, chlorine, bromine, phenyl or trifluoromethyl.

The borate compound is pinacol borane or naphthol borane.

In the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified. The present invention is not limited to any particular substitution site for the substituent.

In a specific embodiment of the invention, the alkyl halide or sulfonate compound is 1-bromooctane, 1-bromohexane, 1-bromoheptane, 1-bromononane bromomethylcyclohexane, 2-cyclohexylbromoethane, 1-bromo-3-methylbutane, 1-bromo-3, 7-dimethyloctane, 1-bromophenyl propane, ethyl 7-bromoheptanoate, ethyl 2- (4- (4-bromobutyl) phenyl) acetate, 5-bromo-2-methyl-2-pentene, 1-bromoethyl benzene, p-trifluoromethylbromoethyl benzene, 3- (2-bromoethyl) thiophene, 5- (2-bromoethyl) -2, 3-dihydrobenzofuran, 2- (2-bromoethyl) -1, 3-dioxane, 2- (2-bromoethyl) -1, 3-dioxane, 3-bromopropyl methyl ether, 3-phenoxybromopropane, 3-benzyloxybromopropane, 2- (3-bromopropoxy) naphthalene, 2- (3-bromopropoxy) tetrahydro-2 h-pyran, 3-bromopropyl-1, 1-dimethylethyl sulfide, 2- (4- (4-bromobutyl) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborole, 1-bromo-4- (4-bromobutyl) benzene, 1- (5-bromopentyl) -1 hydroindole, 9- (5-bromopentyl) -9 hydrocarbazole, bromocyclobutane, bromocyclododecane, and the like, Bromocyclopentane, bromocyclohexane, bromocycloheptane, 4-bromotetrahydropyran, 1-bromo-2-methylcyclohexane, (1R, 2R, 4R) -2-bromo-1-isopropyl-4-methylcyclohexane, 2-bromoindane, exo-2-bromonorbornane, 2-bromooctane, 2-bromoadamantane, 1-Cbz-4-bromopiperidine, 1-Boc-4-bromopiperidine, 1-bromoadamantane, 1-bromocedryl, bromocholesterol, 1-chloroheptane, 1-chlorooctane, 1-chloroethane, 1-chloropropylene, 3-phenoxychloropropane, 2-chloropropane, 4-chlorotetrahydropyran, chlorocyclobutane, 1-iodohexane, hexyl methanesulfonate, (5S, 8S, 9S, 10S, 13S, 14S) -3-bromo-10, 13-dimethylhexadecahydro-17 hydro-cyclopenta [ a ] phenanthren-17-one.

In the present invention, the reaction is preferably carried out under stirring, and the stirring conditions in the present invention are not particularly limited, and may be carried out by a procedure well known to those skilled in the art.

After the reduction reaction is finished, the method also preferably comprises separation, the method does not have any special limitation on the separation, column chromatography is adopted to purify the product, if naphthol borane is used as a boron source in the reaction, pinacol and triethylamine are added to carry out conversion after the reaction is finished, and then column chromatography purification is carried out. In the embodiment of the invention, the separation is not performed in the embodiments 1 to 40, an alkyl boronic acid pinacol ester product system is directly obtained, and the yield of the alkyl boronic acid pinacol ester compound in the product system is analyzed through gas chromatography. If the product system needs to be separated and purified, the separation method is referred to.

The following examples are provided to illustrate the preparation of the borate compounds of the present invention in detail, but they should not be construed as limiting the scope of the present invention.

Example 1 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (noted as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (noted as MTBE, 1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 81%.

The chemical reaction formula of the preparation process is as follows:

。

example 2 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), potassium methoxide (noted as MeOK, 0.2mmol, 14.0 mg), toluene (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34 μ L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure shown in formula 2 a. The yield of the gas chromatography was 6%.

The chemical reaction formula of the preparation process is as follows:

。

example 3 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), sodium methoxide (MeONa, 0.2mmol, 11 mg), toluene (1 mL) and pinacolborane (HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (1 a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under a nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 33%.

The chemical reaction formula of the preparation process is as follows:

。

example 4 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), toluene (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure shown in formula 2 a. The yield of the gas chromatography was 65%.

The chemical reaction formula of the preparation process is as follows:

。

example 5 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), potassium tert-butoxide (noted^tBuOK, 0.2mmol, 22.4 mg), toluene (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added into a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure shown in formula 2 a. The yield of the gas chromatography was 26%.

The chemical reaction formula of the preparation process is as follows:

。

example 6 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), sodium tert-butoxide (noted^tBuONa, 0.2mmol, 19 mg), toluene (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure shown in formula 2 a. The yield of the gas chromatography was 32%.

The chemical reaction formula of the preparation process is as follows:

。

example 7 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), lithium tert-butoxide (note as^tBuOLi, 0.2mmol, 16 mg), toluene (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure shown in formula 2 a. The yield of the gas chromatography was 20%.

The chemical reaction formula of the preparation process is as follows:

。

example 8 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), cesium carbonate (noted as Cs)₂CO₃0.2mmol, 55 mg), toluene (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min and added with 1-bromooctane (noted as HBpin)1a, 0.2mmol, 34 μ L) and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to give a product system containing the compound of formula 2 a. The yield of the gas chromatography was 1%.

The chemical reaction formula of the preparation process is as follows:

。

example 9 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), cesium fluoride (CsF, 0.2mmol, 30.4 mg), toluene (1 mL) and pinacolborane (HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (1 a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under a nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure shown in formula 2 a. The yield of the gas chromatography was 5%.

The chemical reaction formula of the preparation process is as follows:

。

example 10 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), silver acetate (shown as AgOAc, 0.2mmol, 33.4 mg), toluene (1 mL) and pinacolborane (shown as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (shown as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure shown in formula 2 a. The yield of the gas chromatography was 29%.

The chemical reaction formula of the preparation process is as follows:

。

example 11 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), lithium carbonate (lithium carbonateIs described as Li₂CO₃0.2mmol, 15 mg), toluene (1 mL) and pinacolborane (HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (1 a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 6%.

The chemical reaction formula of the preparation process is as follows:

。

example 12 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), lithium hydride (denoted as LiH, 0.2mmol, 1.6 mg), toluene (1 mL) and pinacolborane (denoted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (denoted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under a nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 3%.

The chemical reaction formula of the preparation process is as follows:

。

example 13 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), methyllithium (noted as MeLi, 0.2mmol, 4.4 mg), toluene (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure shown in formula 2 a. The yield of the gas chromatography was 3%.

The chemical reaction formula of the preparation process is as follows:

。

example 14 (cyclopentadiene) titanium trichloride (denoted as CpTiCl)₃0.02mmol, 4.4 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), toluene (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 21%.

The chemical reaction formula of the preparation process is as follows:

。

example 15 bis (t-butylcyclopentadienyl) titanium dichloride (noted^tBuCp₂TiCl₂0.02mmol, 7.2 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), toluene (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 3%.

The chemical reaction formula of the preparation process is as follows:

。

example 16 pentamethylcyclopentadienyltitanium trichloride (denoted Cp TiCl)₃0.02mmol, 5.8 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), toluene (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 1%.

The chemical reaction formula of the preparation process is as follows:

。

example 17 bis (pentamethylcyclopentadienyl) titanium dichloride (noted Cp;)₂TiCl₃0.02mmol, 7.8 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), toluene (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 1%.

The chemical reaction formula of the preparation process is as follows:

。

example 18 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), tetrahydrofuran (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 27%.

The chemical reaction formula of the preparation process is as follows:

。

example 19 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), lithium methoxide (as MeOLi,0.2mmol,7.6 mg), dioxane (1 mL) and pinacolborane (as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min and then added with 1-bromooctane (as 1a, 02mmol, 34 μ L) under nitrogen (1 atm) at 100 ℃ for 8h to obtain a product system containing the compound of formula 2 a. The yield of the gas chromatography was 81%.

The chemical reaction formula of the preparation process is as follows:

。

example 20 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), dichloromethane (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 1%.

The chemical reaction formula of the preparation process is as follows:

。

example 21 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), N-dimethylformamide (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 1%.

The chemical reaction formula of the preparation process is as follows:

。

example 22 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂，0.02mmol，5mg）、Lithium methoxide (noted as MeOLi,0.2mmol,7.6 mg), n-hexane (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under a nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 46%.

The chemical reaction formula of the preparation process is as follows:

。

example 23 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), acetonitrile (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 3%.

The chemical reaction formula of the preparation process is as follows:

。

example 24 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), n-hexane (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under a nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 46%.

The chemical reaction formula of the preparation process is as follows:

。

example 25 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), diethylene glycol dimethyl ether (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 14%.

The chemical reaction formula of the preparation process is as follows:

。

example 26 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), chloroform (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 1%.

The chemical reaction formula of the preparation process is as follows:

。

example 27 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 91%.

The chemical reaction formula of the preparation process is as follows:

。

example 28 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 90 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 93%.

The chemical reaction formula of the preparation process is as follows:

。

example 29 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 80 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 85%.

The chemical reaction formula of the preparation process is as follows:

。

example 30 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.02mmol, 5 mg), lithium methoxide (as MeOLi, 0.15mmol, 5.7 mg), methyl tert-butyl ether (1 mL) and pinacolborane (as HBpin, 0.4mmol, 58. mu.L) were added in sequence to a 38mL pressure resistant tube, stirred for 30min and added1-bromooctane (1 a, 0.2mmol, 34. mu.L) was added and stirred at 80 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure shown in formula 2 a. The yield of the gas chromatography was 57%.

The chemical reaction formula of the preparation process is as follows:

。

example 31 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 60 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 72%.

The chemical reaction formula of the preparation process is as follows:

。

example 32 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 35 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 32%.

The chemical reaction formula of the preparation process is as follows:

。

example 33 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.02mmol, 5 mg), lithium methoxide (noted as MeOLI, 0.1mmol, 3.8 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 80 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 38%.

The chemical reaction formula of the preparation process is as follows:

。

example 34 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.02mmol, 5 mg), lithium methoxide (noted as MeOLI, 0.05mmol, 1.9 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 80 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 4%.

The chemical reaction formula of the preparation process is as follows:

。

example 35 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.02mmol, 5 mg), lithium methoxide (noted as MeOLI, 0.02mmol, 0.76 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 80 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 3%.

The chemical reaction formula of the preparation process is as follows:

。

example 36 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 80 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 89%.

The chemical reaction formula of the preparation process is as follows:

。

example 37 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.005mmol, 1.3 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 80 ℃ for 8h under a nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 72%.

The chemical reaction formula of the preparation process is as follows:

。

example 38 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.002mmol, 0.63 mg), lithium methoxide (as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (as 1a, 0.2mmol, 34. mu.L), and stirred at 80 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a structured compound containing the compound represented by formula 2aThe product system of the compound. The yield of the gas chromatography was 65%.

The chemical reaction formula of the preparation process is as follows:

。

example 39 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 80 ℃ for 12h under a nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 76%.

The chemical reaction formula of the preparation process is as follows:

。

example 40 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 60 ℃ for 24h under a nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 81%.

The chemical reaction formula of the preparation process is as follows:

。

the borate ester compounds with the structure shown in the formula 2a prepared in the embodiments 1-40 are all colorless transparent liquid 1-octane borate pinacol ester, and the characterization data are as follows:¹H NMR (400 MHz, Chloroform-d) δ 1.49 – 1.33 (m, 3H), 1.25 (s, 9H), 1.23 (s, 12H), 0.86 (t, J = 6.7 Hz, 3H), 0.75 (t, J = 7.7 Hz, 2H). ¹³C NMR (101 MHz, Chloroform-d) δ 82.8, 32.4, 31.9, 29.4, 29.2, 24.8, 24.0, 22.7, 14.1.¹¹B NMR (128 MHz, Chloroform-d) δ 34.35。

example 41 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromohexane (noted as 1b, 0.2mmol, 28.2. mu.L), stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and column chromatography was performed using petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound of the structure represented by formula 2b (colorless transparent liquid, 1-hexanylboronic acid pinacol ester). The isolated yield was 83%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 1.47 – 1.35 (m, 2H), 1.27 (ddd, J = 6.5, 3.7, 2.2 Hz, 6H), 1.24 (s, 12H), 0.93 – 0.84 (m, 3H), 0.76 (t, J = 7.7 Hz, 2H). ¹³C NMR (101 MHz, Chloroform-d) δ 82.8, 32.1, 31.6, 29.7, 24.8, 24.0, 22.6, 14.1. ¹¹B NMR (128 MHz, Chloroform-d) δ 34.31。

example 42 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromoheptane (noted as 1c, 0.2mmol, 31.5. mu.L), stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and column chromatography purification was performed with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound of the structure represented by formula 2c (colorless transparent liquid,1-Heptanylboronic acid pinacol ester). The isolated yield was 83%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 1.49 – 1.33 (m, 3H), 1.25 (s, 9H), 1.23 (s, 12H), 0.86 (t, J = 6.7 Hz, 3H), 0.75 (t, J = 7.7 Hz, 2H). ¹³C NMR (101 MHz, Chloroform-d) δ 82.8, 32.4, 31.9, 29.4, 29.2, 24.8, 24.0, 22.7, 14.1.¹¹B NMR (128 MHz, Chloroform-d) δ 34.35。

example 43 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromononane (noted as 1d, 0.2mmol, 31.5. mu.L), stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and column chromatography purification was performed with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound of the structure represented by formula 2d (colorless transparent liquid, 1-nonanylboronic acid pinacol ester). The isolated yield was 89%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 1.51 – 1.33 (m, 2H), 1.25 (s, 12H), 1.24 (s, 12H), 0.87 (t, J = 6.8 Hz, 3H), 0.76 (t, J = 7.8 Hz, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 82.8, 32.4, 31.9, 29.6, 29.4, 29.3, 24.8, 24.0, 22.7, 14.1.¹¹B NMR (128 MHz, Chloroform-d) δ 34.24。

example 44 bis (cyclopentadienyl) titanium dichloride (notedCp₂TiCl₂0.02mmol, 2.5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as Hbpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, bromomethylcyclohexane (noted as 1e, 0.2mmol, 29. mu.L) was added, stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and column chromatography purification was performed using petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound of the structure shown in formula 2e (colorless transparent liquid, 2-methylcyclohexyl boronic acid pinacol ester). The isolated yield was 57%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 1.81 – 1.57 (m, 5H), 1.53 – 1.39 (m, 1H), 1.24 (s, 15H), 1.03 – 0.84 (m, 2H), 0.71 (d, J = 7.1 Hz, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 82.8, 35.9, 34.2, 26.6, 26.3, 24.9.¹¹B NMR (128 MHz, Chloroform-d) δ 34.07。

example 45 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as Hbpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then 2-cyclohexylbromoethane (noted as 1f, 0.2mmol, 31.4. mu.L) was added, stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and column chromatography purification was performed with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound of the structure represented by formula 2f (colorless transparent liquid, 2-ethylcyclohexylboronic acid pinacol ester). The isolated yield was 70%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 1.79 – 1.52 (m, 6H), 1.25 – 1.21 (m, 2H), 1.17 (s, 12H), 1.13 – 1.03 (m, 3H), 0.78 (td, J = 11.6, 2.9 Hz, 2H), 0.69 (dd, J = 9.3, 7.3 Hz, 2H). ¹³C NMR (101 MHz, Chloroform-d) δ 82.8, 40.0, 33.0, 31.4, 26.8, 26.4, 24.8. ¹¹B NMR (128 MHz, Chloroform-d) δ 34.22。

example 46 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromo-3-methylbutane (noted as 1g, 0.2mmol, 25. mu.L), stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and column chromatography purification was performed with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain the structural compound represented by formula 2g (colorless transparent liquid, 2-isopentyl pinacol borate). The isolated yield was 74%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 1.50 – 1.41 (m, 1H), 1.34 – 1.26 (m, 2H), 1.24 (s, 12H), 0.86 (d, J = 6.6 Hz, 6H), 0.79 – 0.70 (m, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 82.8, 32.9, 30.2, 24.8, 22.2.¹¹B NMR (128 MHz, Chloroform-d) δ 34.30。

example 47 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromo-3, 7-dimethyloctane (as 1h, 0.2mmol, 42. mu.L), and stirred at 60 deg.C under nitrogen (1 atm)Stirring for 24h, and purifying by column chromatography with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain compound (colorless transparent liquid, 2- (2, 7-dimethyl octyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) with structure shown in formula 2 h. The isolated yield was 74%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 1.71 – 1.44 (m, 1H), 1.41 – 1.27 (m, 6H), 1.24 (s, 12H), 1.18 – 0.98 (m, 3H), 0.85 (dd, J = 7.7, 6.5 Hz, 9H), 0.80 – 0.59 (m, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 82.8, 39.4, 36.9, 35.0, 31.0, 28.0, 24.8, 24.8, 22.7, 22.6, 19.2.¹¹B NMR (128 MHz, Chloroform-d) δ 34.35. HRMS (ESI) m/z: [M+Na]⁺ calcd for C₁₆H₃₃BNaO₂ ⁺: 291.2466; found: 291.2468。

example 48 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (described as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (described as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromobenzene propane (described as 1h, 0.2mmol, 30.4 μ L), stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and mixed with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound (colorless transparent liquid, 2- (3-phenylpropyl) boronic acid pinacol ester) with a structure shown in formula 2h by column chromatography purification. The isolated yield was 86%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 7.24 – 7.12 (m, 2H), 7.11 – 7.04 (m, 3H), 2.59 – 2.46 (m, 2H), 1.76 – 1.57 (m, 2H), 1.16 (s, 12H), 0.84 – 0.68 (m, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 142.7, 128.5, 128.1, 125.5, 82.9, 38.6, 26.1, 24.8.¹¹B NMR (128 MHz, Chloroform-d) δ 34.13。

example 49 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then ethyl 7-bromoheptanoate (note as 1k, 0.2mmol, 38.8 μ L) was added, stirred under nitrogen (1 atm) at 100 ℃ for 24h, and the mixture was cooled to room temperature using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (2 h) shown in the formula (colorless transparent liquid, 2- (7-ethyl heptanoate) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan). The isolated yield was 47%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 4.11 (q, J = 7.1 Hz, 2H), 2.26 (t, J = 7.6 Hz, 2H), 1.65 – 1.56 (m, 3H), 1.39 (td, J = 6.0, 4.8, 2.7 Hz, 3H), 1.30 (q, J = 3.7 Hz, 5H), 1.23 (s, 12H), 0.75 (t, J = 7.7 Hz, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 173.9, 82.9, 60.1, 34.4, 31.9, 28.9, 24.8, 23.8, 14.2. ¹¹B NMR (128 MHz, Chloroform-d) δ 34.22. HRMS (ESI) m/z: [M+Na]⁺calcd for C₁₅H₂₉BNaO₄ ⁺: 307.2051; found: 307.2054。

example 50 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (noted as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (noted as MeOLi)0.4mmol, 58 μ L) for HBpin were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with ethyl 2- (4- (4-bromobutyl) phenyl) acetate (1 j, 0.2mmol, 63 mg), stirred under nitrogen (1 atm) atmosphere at 100 ℃ for 24h, and the mixture was stirred with petroleum ether/ethyl acetate (5: 1, v/v) as an eluent to obtain a compound (4- ((5- (4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) pentyl) oxy) phenyl propionate) with a structure shown in a formula 2j by column chromatography purification. The isolated yield was 61%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 7.98 (d, J = 8.8 Hz, 2H), 6.89 (d, J = 8.9 Hz, 2H), 4.34 (q, J = 7.1 Hz, 2H), 4.00 (t, J = 6.6 Hz, 2H), 1.80 (dd, J = 8.6, 5.0 Hz, 2H), 1.55 – 1.45 (m, 4H), 1.38 (t, J = 7.1 Hz, 3H), 1.24 (s, 12H), 0.92 – 0.73 (m, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 166.5, 162.9, 131.5, 122.7, 114.2, 82.9, 68.1, 60.5, 28.9, 28.6, 24.8, 23.7, 14.4.¹¹B NMR (128 MHz, Chloroform-d) δ 34.50。

example 51 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (described as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (described as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 5-bromo-2-methyl-2-pentene (described as 1L, 0.2mmol, 26.8 μ L), stirred under nitrogen (1 atm) at 60 ℃ for 24h, and mixed with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (4, 4,5, 5-tetramethyl-2- (4-methylpent-3-en-1-yl) -1,3, 2-dioxaborolan) with a structure shown in a formula 2l by column chromatography purification. The isolated yield was 47%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 5.11 (tt, J = 7.2, 1.5 Hz, 1H), 2.08 (q, J = 7.3 Hz, 2H), 1.66 (s, 3H), 1.60 (s, 3H), 1.24 (s, 12H), 0.82 (t, J = 7.8 Hz, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 130.4, 126.8, 82.9, 25.7, 24.8, 22.5, 17.6.¹¹B NMR (128 MHz, Chloroform-d) δ 34.02. HRMS (ESI) m/z: [M+Na]⁺ calcd for C₁₃H₂₇BNaO₂ ⁺: 233.1683; found: 233.1680。

example 52 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (described as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (described as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromobenzane (described as 1m, 0.2mmol, 27.3 μ L), stirred under nitrogen (1 atm) at 60 ℃ for 24h, and replaced with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound (colorless transparent liquid, 2- (2-phenylethyl) boronic acid pinacol ester) having a structure shown in formula 2 m. The isolated yield was 80%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 7.33 – 7.19 (m, 4H), 7.20 – 7.12 (m, 1H), 2.91 – 2.59 (m, 2H), 1.22 (s, 12H), 1.14 (dd, J = 9.0, 7.4 Hz, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 144.4, 128.2, 128.0, 125.5, 83.1, 30.0, 24.8.¹¹B NMR (128 MHz, Chloroform-d) δ 33.98。

EXAMPLE 53 bis (cyclopentadienyl) titanium dichloride (noteIs Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with p-trifluoromethylbromoethylbenzene (note as 1n, 0.2mmol, 27.3 μ L), stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and replaced with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (2 n) shown in the formula (2- (4- (trifluoromethyl) phenethyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) by column chromatography purification. The isolated yield was 60%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 7.51 (d, J = 7.7 Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H), 2.80 (t, J = 8.1 Hz, 2H), 1.22 (s, 12H), 1.19 – 1.11 (m, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 147.51, 127.31, 126.9 (d, J = 32.1 Hz), 124.8, 124.1 (q, J = 3.8 Hz), 122.10, 82.24, 28.83, 23.78.¹¹B NMR (128 MHz, Chloroform-d) δ 33.84.¹⁹F NMR (376 MHz, Chloroform-d) δ -62.26。

example 54 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 3- (2-bromoethyl) thiophene (note as 1o, 0.2mmol, 38 mg), stirred at 60 ℃ under nitrogen (1 atm) for 24h, and mixed with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (colorless transparent liquid, 2- (thiophene-3-yl) ethyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborole) with a structure shown in a formula 2 o. The isolated yield was 74%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 7.07 (dd, J = 5.1, 1.3 Hz, 1H), 6.89 (dd, J = 5.1, 3.4 Hz, 1H), 6.79 (dt, J = 3.4, 1.1 Hz, 1H), 2.96 (td, J = 8.0, 1.0 Hz, 2H), 1.23 (s, 14H). ¹³C NMR (101 MHz, Chloroform-d) δ 147.8, 126.5, 123.4, 122.6, 83.2, 24.8, 24.3.¹¹B NMR (128 MHz, Chloroform-d) δ 33.77。

example 55 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (described as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (described as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 5- (2-bromoethyl) -2, 3-dihydrobenzofuran (described as 1p, 0.2mmol, 45.4 mg), stirred under nitrogen (1 atm) at 60 ℃ for 24h, and replaced with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (2-ethyl (2, 3-dihydrobenzofuran) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborole) with a structure shown in a formula 2p by column chromatography purification. The isolated yield was 89%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 7.05 (d, J = 1.9 Hz, 1H), 6.94 (ddd, J = 8.1, 1.8, 0.8 Hz, 1H), 6.67 (d, J = 8.1 Hz, 1H), 4.52 (t, J = 8.7 Hz, 2H), 3.16 (t, J = 8.6 Hz, 2H), 2.86 – 2.56 (m, 2H), 1.22 (s, 12H), 1.08 (s, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 158.0, 136.5, 127.3, 126.7, 124.5, 108.7, 83.0, 71.0, 29.8, 29.4, 24.8. ¹¹B NMR (128 MHz, Chloroform-d) δ 33.92. HRMS (ESI) m/z: [M+Na]⁺ calcd for C₁₆H₂₃BNaO₄ ⁺: 297.1632; found: 297.1635。

example 56 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were added in sequence to a 38mL pressure resistant tube, stirred for 30min, then 2- (2-bromoethyl) -1, 3-dioxane (note as 1q, 0.2mmol, 27.5 μ L) was added, stirred under nitrogen (1 atm) at 60 ℃ for 24h, and the mixture was cooled to room temperature in petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound having a structure represented by formula 2q (colorless transparent liquid, 2- (2-ethyl (1, 3-dioxane)) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan). The isolated yield was 79%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 4.46 (t, J = 5.1 Hz, 1H), 4.06 (dd, J = 11.9, 5.0, 1.4 Hz, 2H), 3.72 (dd, J = 11.9, 10.5, 2.6, 1.6 Hz, 2H), 2.04 (dt, J = 13.4, 12.4, 5.0 Hz, 1H), 1.70 (td, J = 7.8, 5.1 Hz, 2H), 1.35 – 1.26 (m, 1H), 1.22 (s, 12H), 0.81 (t, J = 7.7 Hz, 2H). ¹³C NMR (101 MHz, Chloroform-d) δ 103.2, 82.9, 29.5, 25.9, 24.8.¹¹B NMR (128 MHz, Chloroform-d) δ 33.77。

example 57 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, and then 2- (2-bromoethyl) -2-methyl-1, 3-dioxolane (as 1r, 0.2 mmol)L, 28 μ L), stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and extracted with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (colorless transparent liquid, 2- (2-methyl-1, 3-dioxygen heterocycle) ethyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxy boron heterocyclic cyclopentane) with a structure shown in a formula 2 r. The isolated yield was 83%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 3.92 (s, 3H), 1.78 (t, J= 7.9 Hz, 2H), 1.29 (d, J = 8.0 Hz, 4H), 1.24 (s, 12H), 0.81 (t, J = 7.9 Hz, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 110.5, 82.9, 64.8, 33.4, 24.8, 23.7.¹¹B NMR (128 MHz, Chloroform-d) δ 34.00. HRMS (ESI) m/z: [M+Na]⁺ calcd for C₁₂H₂₃BNaO₄ ⁺: 265.1582; found: 265.1584。

example 58 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 3-bromopropylmethyl ether (note as 1s, 0.2mmol, 23 μ L), stirred under nitrogen (1 atm) at 60 ℃ for 24h, and replaced with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (colorless transparent liquid, 2- (3-methoxy propyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborole cyclopentane) with a structure shown in a formula 2 s. The isolated yield was 90%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 3.34 (t, J = 6.6 Hz, 1H), 3.31 (s, 1H), 1.68 (p, J = 7.2 Hz, 2H), 1.24 (d, J = 1.1 Hz, 12H), 0.79 (t, J= 7.7 Hz, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 82.9, 74.6, 58.4, 29.7, 24.8, 24.0. ¹¹B NMR (128 MHz, Chloroform-d) δ 34.07。

example 59 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then 3-phenoxybromopropane (note as 1t, 0.2mmol, 32 μ L) was added, stirred under nitrogen (1 atm) at 60 ℃ for 24h, and the mixture was cooled to room temperature using petroleum ether/ethyl acetate (10: 1, v/v) as eluent to obtain a compound (colorless transparent liquid, 2- (3-phenoxypropyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborole cyclopentane) with a structure shown in formula 2t by column chromatography purification. The isolated yield was 78%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 7.31 – 7.22 (m, 4H), 7.22 – 7.16 (m, 1H), 4.43 (s, 2H), 3.37 (t, J = 6.7 Hz, 2H), 1.67 (p, J = 7.0 Hz, 2H), 1.15 (s, 12H), 0.76 (t, J = 7.8 Hz, 2H). ¹³C NMR (101 MHz, Chloroform-d) δ 138.9, 128.3, 127.6, 127.4, 82.9, 72.7, 72.4, 24.8, 24.2.¹¹B NMR (128 MHz, Chloroform-d) δ 34.18。

example 60 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, and then 3-benzyloxy bromopropane (as 1u, 0.2 mmol)35 μ L) was stirred at 60 ℃ for 24 hours under a nitrogen (1 atm) atmosphere, and the mixture was stirred with petroleum ether/ethyl acetate (30: 1, v/v) as eluent to obtain a compound (colorless transparent liquid, 2- (3- (benzyloxy) propyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) with a structure shown in a formula 2u by column chromatography purification. The isolated yield was 78%.

The chemical reaction formula of the preparation process is as follows:

。

example 61 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 2- (3-bromopropoxy) naphthalene (note as 1v, 0.2mmol, 53 mg), stirred at 60 ℃ under nitrogen (1 atm) for 24h, and mixed with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (2 v) shown in the formula (2- (3- (naphthalene-2-acyloxy) propyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborole) by column chromatography purification. The isolated yield was 79%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 7.83 – 7.67 (m, 3H), 7.42 (ddd, J = 8.2, 6.9, 1.4 Hz, 1H), 7.37 – 7.28 (m, 1H), 7.21 – 7.09 (m, 2H), 4.07 (t, J = 6.7 Hz, 2H), 1.98 (dq, J = 8.0, 6.7 Hz, 2H), 1.27 (s, 12H), 0.98 (t, J = 7.8 Hz, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 157.2, 134.7, 129.2, 127.6, 126.7, 126.2, 123.4, 119.1, 106.8, 83.1, 69.7, 24.9, 23.7.¹¹B NMR (128 MHz, Chloroform-d) δ 34.48。

example 62 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (noted as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirring for 30min, adding 2- (3-bromopropoxy) tetrahydro-2H-pyran (1 w, 0.2mmol, 34 μ L), stirring at 60 deg.C for 24H under nitrogen (1 atm), and purifying by column chromatography with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain compound (colorless transparent liquid, 2- (3- ((tetrahydro-2H-pyran-2-yl) oxy) propyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) with structure shown in formula 2 w. The isolated yield was 78%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 4.58 (dd, J = 4.2, 2.9 Hz, 1H), 3.85 (dd, J = 11.2, 8.0, 3.2 Hz, 1H), 3.67 (dt, J = 9.6, 7.0 Hz, 1H), 3.56 – 3.40 (m, 1H), 3.35 (dt, J = 9.6, 6.7 Hz, 1H), 1.77 – 1.45 (m, 8H), 1.23 (s, 12H), 0.81 (td, J = 7.7, 2.5 Hz, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 98.5, 82.9, 69.2, 62.0, 30.7, 25.5, 24.8, 24.2, 19.5.¹¹B NMR (128 MHz, Chloroform-d) δ 34.26。

example 63 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂，0.01mmol，2.5mg）、Lithium methoxide (denoted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (denoted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then 3-bromopropyl 1, 1-dimethylethyl sulfide (denoted as 1X, 0.2mmol, 42 mg) was added, stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and column chromatography was performed using petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound of the structure represented by formula 2X (colorless transparent liquid, 2- (3- (tert-butyl) propyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan). The isolated yield was 70%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 2.67 – 2.46 (m, 2H), 1.69 (p, J = 7.6 Hz, 2H), 1.31 (s, 9H), 1.24 (s, 12H), 0.89 (t, J = 7.7 Hz, 2H). ¹³C NMR (101 MHz, Chloroform-d) δ 83.0, 41.8, 31.1, 30.8, 24.8. ¹¹B NMR (128 MHz, Chloroform-d) δ 33.98. HRMS (ESI) m/z: [M+Na]⁺ calcd for C₁₃H₂₇BNaO₂S⁺: 281.1717; found: 281.1716。

example 64 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (described as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (described as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then 2- (4- (4-bromobutyl) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan (described as 1y, 0.2mmol, 65 mg) was added, stirred under nitrogen (1 atm) at 60 ℃ for 24h, and the mixture was stirred with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound with a structure shown in a formula 2y (colorless transparent liquid, 2- (4- (4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) butyl) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan). The isolated yield was 20%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 7.83 – 7.60 (m, 2H), 7.19 (d, J = 7.9 Hz, 2H), 2.62 (dd, J = 8.8, 6.8 Hz, 2H), 1.80 – 1.66 (m, 2H), 1.33 (s, 14H), 1.24 (s, 12H), 0.82 (d, J = 8.0 Hz, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 146.2, 134.8, 128.0, 83.6, 82.9, 38.8, 25.9, 24.86, 24.83.¹¹B NMR (128 MHz, Chloroform-d) δ 34.47, 31.66. HRMS (ESI) m/z: [M+Na]⁺ calcd for C₂₁H₃₄B₂NaO₄ ⁺: 409.2692; found: 409.2689。

example 65 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (described as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (described as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromo-4- (4-bromobutyl) benzene (described as 1z, 0.2mmol, 58 mg), stirred under nitrogen (1 atm) at 60 ℃ for 24h, and mixed with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (2- (4- (4-bromophenyl) butyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborole) with a structure shown in a formula 2z by column chromatography purification. The isolated yield was 66%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 7.44 – 7.20 (m, 2H), 7.18 – 6.99 (m, 2H), 2.57 (dt, J = 21.1, 7.7 Hz, 2H), 1.72 – 1.54 (m, 2H), 1.45 (ddd, J = 11.2, 7.6, 5.7 Hz, 2H), 1.23 (s, 12H), 0.92 – 0.71 (m, 2H). ¹³C NMR (101 MHz, Chloroform-d) δ 142.9, 141.8, 131.2, 130.1, 128.4, 128.2, 125.5, 119.2, 82.90, 82.86, 35.8, 35.1, 34.1, 33.9, 24.8, 23.8, 23.6. ¹¹B NMR (128 MHz, Chloroform-d) δ 34.09. HRMS (ESI) m/z: [M+Na]⁺ calcd for C₁₆H₂₄BBrNaO₂ ⁺: 361.0945; found: 361.0945。

example 66 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1- (5-bromopentyl) -1 hydroindole (note as 1aa, 0.2mmol, 53 mg), stirred under nitrogen (1 atm) atmosphere at 60 ℃ for 24h, and the mixture was cooled to room temperature in petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound having a structure represented by formula 2aa (colorless transparent liquid, 1- (5- (4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborole cyclopentane) pentyl)). The isolated yield was 66%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 7.63 (dt, J = 7.9, 1.0 Hz, 1H), 7.35 (dd, J = 8.3, 1.0 Hz, 1H), 7.20 (ddd, J = 8.3, 7.0, 1.2 Hz, 1H), 7.16 – 7.05 (m, 2H), 6.48 (dd, J = 3.1, 0.9 Hz, 1H), 4.12 (t, J = 7.1 Hz, 2H), 1.86 (p, J = 7.3 Hz, 2H), 1.47 (q, J = 7.9 Hz, 2H), 1.36 – 1.30 (m, 2H), 1.23 (s, 12H), 0.79 (t, J = 7.7 Hz, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 136.0, 128.6, 127.7, 121.2, 120.9, 119.1, 109.4, 100.8, 82.9, 46.3, 30.0, 29.6, 24.8, 23.6.¹¹B NMR (128 MHz, Chloroform-d) δ 34.19. HRMS (ESI) m/z: [M+H]⁺ calcd for C₁₉H₂₉BNO₂ ⁺: 314.2286; found: 314.2291。

example 67 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then 9- (5-bromopentyl) -9 hydrocarbazole (note as 1ab, 0.2mmol, 63 mg) was added, stirred under nitrogen (1 atm) at 60 ℃ for 24h, and the mixture was cooled to room temperature using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (colorless transparent liquid, 9- (5- (4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborole) pentyl) -9H carbazole) with a structure shown in a formula 2 ab) through column chromatography purification. The isolated yield was 71%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 8.01 (d, J = 7.7 Hz, 1H), 7.43 – 7.26 (m, 4H), 7.13 (ddd, J = 8.0, 6.9, 1.2 Hz, 2H), 4.21 (t, J = 7.3 Hz, 2H), 1.80 (p, J = 7.3 Hz, 2H), 1.46 – 1.27 (m, 2H), 1.10 (s, 12H), 0.68 (t, J = 7.5 Hz, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 140.5, 125.5, 122.8, 120.3, 118.6, 108.7, 82.9, 43.1, 29.9, 28.8, 24.8, 23.8. ¹¹B NMR (128 MHz, Chloroform-d) δ 33.82. HRMS (ESI) m/z: [M+Na]⁺ calcd for C₂₃H₃₀BNNaO₂ ⁺: 386.2262; found: 386.2266。

example 68 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), potassium carbonate (noted as K)₂CO₃0.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then bromocyclobutane (1 ac, 0.2mmol, 17. mu.L) was added, stirred at 80 ℃ for 24h under nitrogen (1 atm) atmosphere, and the reaction was quenchedAfter completion, triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg) were added and the mixture was stirred at room temperature for 1 hour. Then, the compound with the structure shown in the formula 2ac (colorless transparent liquid, 2-cyclobutyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborole) is obtained by column chromatography purification with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent. The isolated yield was 95%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 2.24 – 1.92 (m, 6H), 1.25 (s, 12H).¹³C NMR (101 MHz, Chloroform-d) δ 82.9, 24.8, 23.9, 22.7.¹¹B NMR (128 MHz, Chloroform-d) δ 33.91。

example 69 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), potassium carbonate (noted as K)₂CO₃0.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (noted HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, bromocyclopentane (noted 1ab, 0.2mmol, 21. mu.L) was added, stirred under nitrogen (1 atm) atmosphere at 80 ℃ for 24h, triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg) were added after the reaction was complete, and stirred at room temperature for 1 h. Then using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to carry out column chromatography purification to obtain a compound (colorless transparent liquid, 2-cyclopentyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) with a structure shown in a formula 2 ab. The isolated yield was 92%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 1.80 – 1.70 (m, 2H), 1.58 (dd, J = 5.3, 1.2 Hz, 2H), 1.53 – 1.40 (m, 4H), 1.24 (s, 12H), 1.16 (d, J = 8.7 Hz, 1H).¹³C NMR (101 MHz, Chloroform-d) δ 82.8, 28.5, 26.8, 24.7.¹¹B NMR (128 MHz, Chloroform-d) δ 34.73。

example 70 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), potassium carbonate (noted as K)₂CO₃0.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (denoted as HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then bromocyclohexane (denoted as 1ae, 0.2mmol, 24. mu.L) was added, stirred under nitrogen (1 atm) atmosphere at 80 ℃ for 24h, after the reaction was complete triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg) were added, and stirred at room temperature for 1 h. Then, the compound with the structure shown in the formula 2ae (colorless transparent liquid, 2-cyclohexyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborole) is obtained by column chromatography purification with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent. The isolated yield was 57%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 1.45 – 1.34 (m, 2H), 1.29 – 1.25 (m, 4H), 1.24 (s, 12H), 0.92 – 0.83 (m, 3H), 0.76 (t, J = 7.7 Hz, 2H).¹³C NMR (101 MHz, Chloroform-d) δ 82.8, 32.1, 31.6, 24.8, 24.0, 22.6, 14.1.¹¹B NMR (128 MHz, Chloroform-d) δ 34.27。

example 71 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), potassium carbonate (noted as K)₂CO₃0.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, bromocycloheptane (1 af, 0.2mmol, 28. mu.L) was added, stirred at 80 ℃ for 24h under nitrogen (1 atm) atmosphere, and reacted to form a precipitateAfter completion, triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg) were added and the mixture was stirred at room temperature for 1 hour. Then using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to carry out column chromatography purification to obtain the compound with the structure shown in the formula 2af (colorless transparent liquid, 2-cycloheptyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolan). The isolated yield was 78%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 1.97 – 1.61 (m, 4H), 1.57 – 1.40 (m, 8H), 1.23 (s, 12H), 1.08 (q, J = 4.8 Hz, 1H).¹³C NMR (101 MHz, Chloroform-d) δ 82.8, 29.6, 29.0, 28.4, 24.7.¹¹B NMR (128 MHz, Chloroform-d) δ 34.55。

example 72 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), potassium carbonate (noted as K)₂CO₃0.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 4-bromotetrahydropyran (1 ag, 0.2mmol, 23. mu.L), stirred under nitrogen (1 atm) at 80 ℃ for 24h, after the reaction was complete, added with triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then, the compound with the structure shown in the formula 2ag (colorless transparent liquid, 2- (tetrahydro-2H-pyran) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborocycloborolane) is obtained by column chromatography purification with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent. The isolated yield was 79%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 3.81 (d, J = 11.2 Hz, 2H), 3.45 (dd, J = 12.7, 6.4, 4.8 Hz, 2H), 1.61 (td, J = 7.5, 6.8, 3.8 Hz, 4H), 1.23 (s, 12H), 1.18 (m, 1H).¹³C NMR (101 MHz, Chloroform-d) δ 83.1, 68.8, 27.6, 24.7.¹¹B NMR (128 MHz, Chloroform-d) δ 33.75。

example 73 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), potassium carbonate (noted as K)₂CO₃0.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (denoted as HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromo-2-methylcyclohexane (denoted as 1ah, 0.2mmol, 28. mu.L), stirred under nitrogen (1 atm) at 80 ℃ for 24h, after the reaction was complete, added with triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then, the compound of formula 2ah (colorless transparent liquid, 2- (1-methylcyclohexyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) was purified by column chromatography using petroleum ether/ethyl acetate (40: 1, v/v) as an eluent. The isolated yield was 68%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 1.77 – 1.59 (m, 4H), 1.48 – 1.38 (m, 2H), 1.24 (d, J = 3.0 Hz, 12H), 0.87 (d, J = 6.5 Hz, 3H), 0.64 – 0.55 (m, 1H).¹³C NMR (101 MHz, Chloroform-d) δ 82.7, 36.1, 33.3, 28.0, 26.8, 26.5, 24.8, 24.6, 22.9.¹¹B NMR (128 MHz, Chloroform-d) δ 34.23. HRMS (ESI) m/z: [M+Na]⁺ calcd for C₁₃H₂₅BNaO₂ ⁺: 247.1840; found: 247.1844。

example 74 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), potassium carbonate (Ji)Is K₂CO₃0.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and borane naphthol (HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then (1R, 2R, 4R) -2-bromo-1-isopropyl-4-methylcyclohexane (1 ai, 0.2mmol, 44 mg) was added, stirred under nitrogen (1 atm) at 80 ℃ for 24h, after the reaction was complete triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg) were added, and stirred at room temperature for 1 h. Then, the compound with the structure shown in the formula 2ai (colorless transparent liquid, 2- (2-isopropyl-5-methylcyclohexyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) is obtained by column chromatography purification with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent. The isolated yield was 77%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 1.79 – 1.67 (m, 1H), 1.68 – 1.57 (m, 3H), 1.23 (s, 15H), 0.90 (d, J = 6.9 Hz, 4H), 0.84 (d, J = 6.5 Hz, 4H), 0.77 (d, J = 6.9 Hz, 3H).¹³C NMR (101 MHz, Chloroform-d) δ 82.7, 43.8, 37.2, 35.4, 33.5, 32.0, 26.0, 24.8, 24.7, 22.7, 21.7, 16.5.¹¹B NMR (128 MHz, Chloroform-d) δ 33.76。

example 75 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), potassium carbonate (noted as K)₂CO₃0.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (denoted as HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 2-bromohydrindene (denoted as 1aj, 0.2mmol, 39 mg), stirred under nitrogen (1 atm) at 80 ℃ for 24h, after the reaction was complete, added with triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to carry out column chromatography purification to obtain a compound (without a structure shown in a formula 2 aj)A colored transparent liquid, 2- (2, 3-dihydro-1 hydro-indene) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan). The isolated yield was 59%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 7.21 (dd, J = 5.3, 3.3 Hz, 2H), 7.12 (dd, J = 5.5, 3.2 Hz, 2H), 3.18 – 2.82 (m, 4H), 1.89 (t, J = 9.8 Hz, 1H), 1.27 (s, 12H).¹³C NMR (101 MHz, Chloroform-d) δ 144.4, 125.9, 124.2, 83.2, 35.1, 24.8.¹¹B NMR (128 MHz, Chloroform-d) δ 34.59。

example 76 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), potassium carbonate (noted as K)₂CO₃0.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (noted as HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with external 2-bromonorbornane (noted as 1ak, 0.2mmol, 24. mu.L), stirred under nitrogen (1 atm) atmosphere at 80 ℃ for 24h, after the reaction was over, added with triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to carry out column chromatography purification to obtain a compound (colorless transparent liquid, 2- ((1S, 4S) -bicyclo [ 2.2.1) with a structure shown in a formula 2ak]Heptan-2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan). The isolated yield was 80%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 2.35 – 2.13 (m, 2H), 1.58 – 1.44 (m, 3H), 1.38 – 1.28 (m, 1H), 1.24 (s, 4H), 1.22 (s, 12H), 1.16 – 1.15 (m, 1H).¹³C NMR (101 MHz, Chloroform-d) δ 82.9, 82.8, 39.0, 38.7, 38.1, 37.1, 36.7, 32.2, 29.9, 29.3, 24.7.¹¹B NMR (128 MHz, Chloroform-d) δ 34.14。

example 77 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), potassium carbonate (noted as K)₂CO₃0.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 2-bromooctane (1 al, 0.2mmol, 34. mu.L), stirred at 80 ℃ for 24h under nitrogen (1 atm) atmosphere, after the reaction was complete, added with triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to carry out column chromatography purification to obtain a compound with a structure shown in a formula 2al (colorless transparent liquid, 2-octyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolan). The isolated yield was 58%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 1.48 – 1.37 (m, 1H), 1.31 – 1.25 (m, 9H), 1.23 (s, 12H), 0.96 (s, 3H), 0.90 – 0.83 (m, 3H).¹³C NMR (101 MHz, Chloroform-d) δ 82.7, 33.3, 31.9, 29.5, 24.8, 24.8, 24.7, 22.6, 15.5, 14.1.¹¹B NMR (128 MHz, Chloroform-d) δ 34.59。

example 78 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), potassium carbonate (noted as K)₂CO₃0.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 2-bromoadamantane (1 am, 0.2mmol, 44 mg), stirred at 80 ℃ under nitrogen (1 atm) for 24h, added after the reaction was completeTriethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg) were added and stirred at room temperature for 1 h. Then, the compound with the structure shown in the formula 2am (colorless transparent liquid, 2-adamantyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) is obtained by column chromatography purification with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent. The isolated yield was 90%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 2.08 – 2.00 (m, 2H), 1.92 – 1.58 (m, 12H), 1.40 – 1.31 (m, 1H), 1.24 (s, 12H).¹³C NMR (101 MHz, Chloroform-d) δ 82.7, 39.4, 37.8, 36.3, 29.3, 28.3, 28.1, 24.8.¹¹B NMR (128 MHz, Chloroform-d) δ 34.17。

example 79 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), potassium carbonate (noted as K)₂CO₃0.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and borane naphthol (noted as HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-Cbz-4-bromopiperidine (noted as 1an, 0.2mmol, 44. mu.L), stirred under nitrogen (1 atm) atmosphere at 80 ℃ for 24h, after the reaction was complete, added with triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then, the compound represented by the formula 2an (4- (2-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborole cyclopentyl) piperidine-1-carboxylic acid benzyl ester) is obtained by column chromatography purification with petroleum ether/ethyl acetate (20: 1, v/v) as an eluent. The isolated yield was 78%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 7.46 – 7.28 (m, 5H), 5.11 (s, 2H), 3.87 (d, J = 13.2 Hz, 2H), 3.17 – 2.94 (m, 2H), 1.65 (s, 2H), 1.61 – 1.46 (m, 2H), 1.23 (s, 12H), 1.13 (td, J = 10.3, 5.1 Hz, 1H).¹³C NMR (101 MHz, Chloroform-d) δ 155.3, 128.4, 127.8, 127.8, 83.2, 66.8, 45.1, 24.8.¹¹B NMR (128 MHz, Chloroform-d) δ 33.65。

example 80 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), potassium carbonate (noted as K)₂CO₃0.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and borane naphthol (noted HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-Boc-4-bromopiperidine (noted 1ao, 0.2mmol, 53 mg), stirred under nitrogen (1 atm) atmosphere at 80 ℃ for 24h, after the reaction was complete triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then, the mixture was purified by column chromatography using petroleum ether/ethyl acetate (20: 1, v/v) as an eluent to give a compound having a structure represented by formula 2ao (colorless transparent liquid, 1-carboxylic acid tert-butyl ester-2- (4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborohetero ring) piperidine). The isolated yield was 36%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 3.90 – 3.67 (m, 2H), 2.92 (ddd, J = 13.4, 10.2, 3.2 Hz, 2H), 1.63 (ddt, J = 12.4, 8.4, 3.6 Hz, 9H), 1.44 (s, 12H), 1.23 (s, 6H), 1.17 – 1.03 (m, 1H).¹³C NMR (101 MHz, Chloroform-d) δ 154.9, 83.1, 79.0, 28.5, 27.0, 24.8.¹¹B NMR (128 MHz, Chloroform-d) δ 34. 04。

example 81 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), potassium carbonate (noted as K)₂CO₃, 0.2mmol, 26.7mg）、Methyl tert-butyl ether (1 mL) and naphthol borane (described as HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromoadamantane (described as 1ap, 0.2mmol, 53 mg), stirred at 80 ℃ under nitrogen (1 atm) for 24h, after the reaction was complete, added with triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then, the compound with the structure shown in the formula 2ap (white solid, 2- ((3 r, 5r, 7 r) -adamantyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) is obtained by column chromatography purification with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent. The isolated yield was 63%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 1.84 (dd, J = 6.0, 3.0 Hz, 3H), 1.75 (d, J = 3.1 Hz, 12H), 1.20 (s, 12H).¹³C NMR (101 MHz, Chloroform-d) δ 82.6, 38.0, 37.5, 27.6, 24.6.¹¹B NMR (128 MHz, Chloroform-d) δ 33.60。

example 82 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), potassium carbonate (noted as K)₂CO₃0.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and borane naphthol (HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromocedrol (1 aq, 0.2mmol, 56.8 mg), stirred under nitrogen (1 atm) at 80 ℃ for 24h, after the reaction was complete, added with triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then, the compound with the structure shown in the formula 2aq (colorless transparent liquid, 2- ((3R, 3aS, 6S, 7S, 8 aS) -3,6,8, 8-tetramethyl-1-hydro-3 a, 7-formyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) is obtained by column chromatography purification with petroleum ether/ethyl acetate (40: 1, v/v) aS an eluent. The isolated yield was 66%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 1.88 – 1.69 (m, 5H), 1.61 (td, J = 7.4, 6.0 Hz, 2H), 1.53 – 1.29 (m, 7H), 1.24 (d, J = 5.3 Hz, 12H), 1.13 (s,3H), 1.02 (d, J = 7.3 Hz, 3H), 0.92 (s, 3H), 0.82 (d, J = 7.1 Hz, 3H).¹³C NMR (101 MHz, Chloroform-d) δ 82.8, 57.8, 56.3, 54.4, 47.3, 44.1, 42.5, 39.3, 37.1, 35.4, 29.0, 27.1, 25.5, 24.9, 24.5, 21.7, 15.4.¹¹B NMR (128 MHz, Chloroform-d) δ 34.63. HRMS (ESI) m/z: [M+Na]⁺ calcd for C₂₁H₃₇BNaO₂ ⁺: 355.2779; found: 355.2777。

example 83 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), potassium carbonate (noted as K)₂CO₃0.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and borane naphthol (HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min and then added (5S, 8S, 9S, 10S, 13S, 14S) -3-bromo-10, 13-dimethylhexadecahydro-17 hydro-cyclopentyl [ a ]]Phenanthren-17-one (denoted as 1ar, 0.2mmol, 70 mg) was stirred at 80 ℃ for 24h under nitrogen (1 atm), and after completion of the reaction, triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg) were added and stirred at room temperature for 1 h. Then using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to carry out column chromatography purification to obtain a compound (colorless transparent liquid, 5S, 8S, 9S, 10S, 13S, 14S) -10, 13-dimethyl-3- (4, 4,5, 5-tetramethyl-1, 3, 2-dioxybenzofuran-2-yl) hexadecahydro-17H-cyclopentane [ a ] with a structure shown in formula 2ar]Phenanthren-17-one). The isolated yield was 66%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 3.61 (t, J = 8.5 Hz, 1H), 2.03 (ddd, J = 9.5, 5.8, 4.1 Hz, 1H), 1.82 – 1.50 (m, 8H), 1.45 – 1.32 (m, 5H), 1.22 (s, 12H), 1.09 – 0.98 (m, 2H), 0.97 – 0.81 (m, 5H), 0.78 (s, 3H), 0.72 (d, J = 3.0 Hz, 3H). ¹³C NMR (101 MHz, Chloroform-d) δ 125.8, 82.7, 82.0, 54.8, 51.2, 47.9, 43.0, 39.5, 36.8, 36.2, 35.6, 31.7, 30.5, 30.1, 28.8, 24.7, 23.4, 23.4, 20.4, 12.4, 11.1. ¹¹B NMR (128 MHz, Chloroform-d) δ 35.42。

example 84 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), potassium carbonate (noted as K)₂CO₃0.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and borane naphthol (denoted as HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with bromocholesterol (denoted as 1as, 0.2mmol, 90 mg), stirred under nitrogen (1 atm) atmosphere at 80 ℃ for 24h, after the reaction was complete, added with triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to carry out column chromatography purification to obtain the compound with the structure shown in the formula 2as (colorless transparent liquid, 2- (3 a, 6 a-dimethyl-3- (6-methylheptan-2-yl) -2,3,3a, 4,5,5a, 6,6a, 7,8,9,10,11a, 11 b-tetradecahydro-1H-cyclopentane [ a ] as]Anthracen-9-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan). The isolated yield was 66%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 5.26 (d, J = 5.0 Hz, 1H), 2.20 (td, J = 13.8, 2.8 Hz, 1H), 2.10 – 1.89 (m, 6H), 1.83 (tq, J = 14.8, 5.7, 4.3 Hz, 13H), 1.70 – 1.31 (m, 12H), 1.23 (s, 7H), 1.15 – 1.03 (m, 7H), 0.99 (s, 3H), 0.91 (d, J = 6.5 Hz, 3H), 0.86 (d, J = 6.7 Hz, 6H), 0.67 (s, 3H).¹³C NMR (101 MHz, Chloroform-d) δ 143.7, 118.5, 82.7, 56.8, 56.2, 50.6, 42.3, 40.9, 39.9, 39.5, 37.3, 36.2, 35.8, 33.8, 31.9, 28.2, 28.0, 24.7, 24.3, 24.1, 23.9, 22.8, 22.6, 20.8, 19.5, 18.7, 11.9.¹¹B NMR (128 MHz, Chloroform-d) δ 34.85. HRMS (ESI) m/z: [M+Na]⁺ calcd for C₃₃H₅₇BNaO₂ ⁺: 519.4344; found: 519.4353。

example 85 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were added in this order to a 38mL pressure resistant tube, stirred for 30min, then added with 1-chloroheptane (note as 1at, 0.2mmol, 31 μ L), stirred under nitrogen (1 atm) at 100 ℃ for 24h, and replaced with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound having a structure represented by formula 2at (a colorless transparent liquid, 1-heptanylboronic acid pinacol ester). The isolated yield was 55%.

The chemical reaction formula of the preparation process is as follows:

。

example 86 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (as HBpin, 0.4mmol, 58. mu.L) were added in this order to a 38mL pressure resistant tube and stirredAfter 30min, 1-chlorooctane (1 au, 0.2mmol, 34 μ L) was added, stirred at 100 ℃ for 24h under nitrogen (1 atm) atmosphere, and purified by column chromatography using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to give a compound of the structure shown by formula 2au (colorless transparent liquid, 1-heptanylboronic acid pinacol ester). The isolated yield was 69%.

The chemical reaction formula of the preparation process is as follows:

。

example 87 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-chloroethane (as 1av, 0.2mmol, 27. mu.L), stirred at 100 ℃ for 24h under nitrogen (1 atm) atmosphere, and column chromatography purification was performed using petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound of the structure represented by formula 2av (colorless transparent liquid, 2- (2-phenylethyl) pinacol borate). The isolated yield was 84%.

The chemical reaction formula of the preparation process is as follows:

。

example 88 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-chloropropane (note as 1aw, 0.2mmol, 30 μ L), stirred under nitrogen (1 atm) at 100 ℃ for 24h, and mixed with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound (colorless transparent liquid, 2- (3-phenylpropyl) boronic acid pinacol ester) having a structure shown in formula 2 aw. The isolated yield was 86%.

The chemical reaction formula of the preparation process is as follows:

。

example 89 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 3-phenoxychloropropane (note as 1ax, 0.2mmol, 32 μ L), stirred at 100 ℃ for 24h under nitrogen (1 atm) atmosphere, and mixed with petroleum ether/ethyl acetate (10: 1, v/v) as eluent to obtain compound (colorless transparent liquid, 2- (3-phenoxypropyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaboroza) with structure shown in formula 2ax by column chromatography purificationCyclopentane). The isolated yield was 58%.

The chemical reaction formula of the preparation process is as follows:

。

example 90 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 2-chloropropane (note as 1ay, 0.2mmol, 30 μ L), stirred under nitrogen (1 atm) at 100 ℃ for 24h, and replaced with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (colorless transparent liquid, 2-phenylpropyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborocyclopentane) with the structure shown in the formula 2ay by column chromatography purification. The isolated yield was 41%.

The chemical reaction formula of the preparation process is as follows:

。

the characterization data are:¹H NMR (400 MHz, Chloroform-d) δ 7.40 – 7.04 (m, 5H), 2.81 (dd, J = 13.6, 7.5 Hz, 1H), 2.56 (td, J = 14.4, 13.6, 8.2 Hz, 1H), 1.44 – 1.30 (m, 1H), 1.18 (d, J = 4.4 Hz, 12H), 0.96 (d, J = 7.4 Hz, 3H).¹³C NMR (101 MHz, Chloroform-d) δ 142.4, 128.9, 128.0, 125.5, 83.0, 39.0, 24.8, 24.7, 24.7, 15.2.¹¹B NMR (128 MHz, Chloroform-d) δ 34.45。

example 91 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 4-chlorotetrahydropyran (note as 1az, 0.2mmol, 23 μ L), stirred under nitrogen (1 atm) at 100 ℃ for 24h, and replaced with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (2-tetrahydro-2-hydropyran) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborocycloborolane) with a structure shown in a formula 2 az. The isolated yield was 68%.

The chemical reaction formula of the preparation process is as follows:

。

example 92 bis (cyclopentadienyl) titanium dichloride (noted Cp)₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, and after stirring for 30min, chlorocyclobutane (note as 1aba, 0.2mmol, 17 μ L) was added, and the mixture was stirred under nitrogen (1 atm) at 100 ℃ for 24h to obtain a solution of petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (colorless transparent liquid, 2-cyclobutyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborole cyclopentane) with a structure shown in formula 2 aba. The isolated yield was 88%.

The chemical reaction formula of the preparation process is as follows:

。

example 93 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were added in sequence to a 38mL pressure resistant tube, stirred for 30min, then added with 1-iodohexane (note as 1abb, 0.2mmol, 30 μ L), stirred under nitrogen (1 atm) atmosphere at 50 ℃ for 24h, and mixed with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound having a structure represented by formula 2abb (colorless transparent liquid, 1-hexanylboronic acid pinacol ester). The yield of the gas chromatography was 95%.

The chemical reaction formula of the preparation process is as follows:

。

example 94 bis (cyclopentadienyl) titanium dichloride (noted Cp₂TiCl₂0.01mmol, 2.5 mg), lithium methoxide (as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (as HBpin, 0.4mmol, 58. mu.L) were added in sequence to a 38mL pressure resistant tube, stirred for 30min and addedHexyl methanesulfonate (noted as 1abc, 0.2mmol, 34. mu.L) was added, stirred at 100 ℃ for 24h under nitrogen (1 atm) atmosphere, and purified by column chromatography using petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to give a compound of the structure represented by formula 2abc (colorless transparent liquid, 1-hexanylboronic acid pinacol ester). The yield of the gas chromatography was 59%.

The chemical reaction formula of the preparation process is as follows:

。

the foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims

1. A method for directly preparing alkyl borate compounds from alkyl halide or sulfonate compounds is characterized by comprising the following steps: in a protective atmosphere, mixing a titanium metal catalyst, an alkali compound, a borate compound and an alkyl halide or sulfonate compound, and reacting at 35-100 ℃ for 8-24 hours, namely directly converting the alkyl halide or sulfonate compound into an alkyl boronic acid pinacol ester compound; the molar ratio of the alkyl halide or sulfonate compound, the titanium metal catalyst, the alkali compound and the borate compound is 1: 0.05-0.1: 0.25-1: 2-3; the alkyl halide or sulfonate compound is 1-bromooctane, 1-bromohexane, 1-bromoheptane, 1-bromononane, bromomethylcyclohexane, 2-cyclohexylbromoethane, 1-bromo-3-methylbutane, 1-bromo-3, 7-dimethyloctane, 1-bromophenylpropane, 7-bromoheptanoic acid ethyl ester, 2- (4- (4-bromobutyl) phenyl) acetic acid ethyl ester, 5-bromo-2-methyl-2-pentene, 1-bromophenylethane, p-trifluoromethylbromoethylbenzene bromide, 3- (2-bromoethyl) thiophene, 5- (2-bromoethyl) -2, 3-dihydrobenzofuran, 2- (2-bromoethyl) -1, 3-dioxane, 1-bromoheptane, 1-bromononane, bromomethylcyclohexane, 2-cyclohexylbromoethylethane, 1-bromoethylbenzene bromide, 3-bromoethylbenzene bromide, 5- (2-bromoethyl) -2, 3-dihydrobenzofuran, 2- (2-bromoethyl) -1, 3-dioxane, or a mixture thereof, 2- (2-bromoethyl) -1, 3-dioxane, 3-bromopropylmethyl ether, 3-phenoxybromopropane, 3-benzyloxybromopropane, 2- (3-bromopropoxy) naphthalene, 2- (3-bromopropoxy) tetrahydro-2 hydro-pyran, 3-bromopropyl-1, 1-dimethylethyl sulfide, 2- (4- (4-bromobutyl) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborole, 1-bromo-4- (4-bromobutyl) benzene, 1- (5-bromopentyl) -1 hydroindole, 9- (5-bromopentyl) -9 hydrocarbazole, bromocyclobutane, bromocyclopentane, bromocyclohexane, dimethylmethane, and dimethylmethane, Bromocycloheptane, 4-bromotetrahydropyrane, 1-bromo-2-methylcyclohexane, (1R, 2R, 4R) -2-bromo-1-isopropyl-4-methylcyclohexane, 2-bromoindane, exo-2-bromonorbornane, 2-bromooctane, 2-bromoadamantane, 1-Cbz-4-bromopiperidine, 1-Boc-4-bromopiperidine, 1-bromoadamantane, 1-bromocedranol, bromocholesterol, 1-chloroheptane, 1-chlorooctane, 1-chloroethane, 1-chloropropane, 3-phenoxychloropropane, 2-chloropropane, 4-chlorotetrahydropyrane, chlorocyclobutane, 1-iodohexane, hexyl methanesulfonate, (5S, 8S, 9S, 10S, 13S, 14S) -3-bromo-10, 13-dimethylhexadecahydro-17 h-cyclopenta [ a ] phenanthren-17-one; the titanium metal catalyst is one of bis (cyclopentadienyl) titanium dichloride, (cyclopentadienyl) titanium trichloride, bis (tert-butylcyclopentadienyl) titanium dichloride, pentamethylcyclopentadienyl titanium trichloride and bis (pentamethylcyclopentadienyl) titanium dichloride; the borate compound is pinacol borane or naphthol borane; the alkali compound is one of potassium methoxide, sodium methoxide, lithium methoxide, potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, cesium carbonate, cesium fluoride, silver acetate, lithium carbonate, lithium hydride and methyllithium; the protective atmosphere refers to nitrogen atmosphere or argon atmosphere, and the pressure is 1 atm.

2. The method for directly preparing alkyl borate compounds from alkyl halide or sulfonate compounds as claimed in claim 1, wherein: an organic solvent is also added in the mixing process of the titanium metal catalyst, the alkali compound, the borate compound and the alkyl halide or sulfonate compound; the molar ratio of the alkyl halide or sulfonate compound to the organic solvent is 0.2 mmol: 1 mL.

3. The method for directly preparing alkyl borate compounds from alkyl halide or sulfonate compounds as claimed in claim 1 or 2, wherein: the organic solvent is one of N-hexane, dioxane, chloroform, N-dimethylformamide, ethyl acetate, diethylene glycol dimethyl ether, methyl tert-butyl ether, tetrahydrofuran, dichloromethane, acetonitrile and toluene.