A kind of alkenyl borate and its preparation method and application

Abstract

The invention discloses an alkenyl borate and a preparation method and application thereof. The preparation method of the alkenyl borate comprises the following steps: in an inert atmosphere, reacting a compound of formula (I) under the action of a cobalt catalyst, a ligand, a boron reagent and a base to obtain a compound of formula (II); the ligand comprises a cation and an anion, and the cation of the ligand is represented by formula (III); the method uses a cobalt catalyst to catalyze the hydroboration of alkynes; the cobalt catalyst is cheap, readily available and environmentally friendly, avoids the use of toxic and expensive heavy metal catalysts, and develops a cheap, readily available and environmentally friendly catalyst; the method is applicable to various types of alkynes, has a wide range of substrate applicability, and can realize efficient and highly selective hydroboration reactions of various types of alkynes; the method can be used for large-scale preparation of alkenyl borate, and the problem of a significant decrease in yield will not occur during scale-up experiments.

Description

Technical Field

[0001] The present invention relates to the technical field of organic compound synthesis, and in particular to an alkenyl borate ester and a preparation method and application thereof. Background Art

[0002] Organic borate esters, with their low toxicity and functional group compatibility, are widely used building blocks in organic synthesis. Specifically configured alkenyl boron compounds play a crucial role in various cross-coupling reactions for the synthesis of stereoselective functionalized alkenes. However, the selective synthesis of alkenyl borate esters with specific stereoselectivity is challenging. Conventional methods for synthesizing stereoselective alkenyl borate esters typically require the use of large amounts of precious metals as catalysts, which are costly and difficult to recycle and reuse. Therefore, the goal of achieving efficient, highly selective, and broadly applicable hydroboration methods using inexpensive catalysts has become a key research priority.

[0003] Related art discloses a selective hydroboration reaction of alkynes catalyzed by cobalt complexes with radical imine ligands (Formula 1). This reaction can achieve highly selective hydroboration of alkyl and some aryl alkynes to form Z-alkenyl borate esters, marking the first use of inexpensive cobalt metal to achieve selective hydroboration to prepare alkenyl borate esters. However, the complex nature of the ligands and their presence of free radical-active centers limit their application in synthesis.

[0004]

[0005] Related technologies have also been developed using copper catalysts and phosphorus ligands (Formula 2) to achieve the hydroboration of aryl olefins. However, this method is only applicable to aryl alkynes, not alkyl alkynes. Furthermore, the reaction has poor selectivity and cannot selectively produce Z-alkenyl borate esters, limiting its application value.

[0006]

[0007] There is also a related technology that uses iron as a catalyst (Formula 3) and utilizes a tridentate pincer ligand to efficiently convert various aromatic alkyne compounds into Z-alkenyl borate esters. However, the need to use deuterated benzene as a solvent limits its practical application.

[0008]

[0009] Some scholars have also reported a hydroboration reaction using an iron pincer complex as a catalyst (Formula 4).

[0010]

[0011] Although some achievements have been made in the selective hydroboration of alkynes, it usually requires the use of toxic noble metals or expensive and complex ligands that require multi-step synthesis, which to some extent limits the practical application of the selective hydroboration of alkynes, especially large-scale preparation. Summary of the Invention

[0012] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention provides a method for preparing alkenyl borate esters. This method utilizes a cobalt catalyst for catalytic hydroboration of alkynes. The cobalt catalyst is inexpensive, readily available, and environmentally friendly, avoiding the use of toxic and expensive heavy metal catalysts and developing an inexpensive, readily available, and environmentally friendly catalyst. Furthermore, the method is applicable to various types of alkynes, has a wide range of substrates, and can achieve efficient and highly selective hydroboration reactions of various alkynes. Furthermore, the method can be used for large-scale preparation of alkenyl borate esters without significantly decreasing yields during scale-up experiments.

[0013] The object of the present invention is to provide a method for preparing alkenyl borate, comprising the following steps:

[0014] In an inert atmosphere, the compound of formula (I) The compound of formula (II) is obtained by reacting with a cobalt catalyst, a ligand, a boron reagent and a base.

[0015] wherein R1 is selected from hydrogen, heterocycle, substituted or unsubstituted aryl, substituted or unsubstituted hydrocarbon;

[0016] The ligand includes a cation and an anion, and the cation of the ligand is shown in formula (III):

[0017]

[0018] Wherein, R2 and R3 are independently selected from C 1～4 alkyl;

[0019] The anion of the ligand is selected from at least one of halide ion, tetrafluoroborate ion, hexafluorophosphate ion, trifluoromethanesulfonate ion, acetate ion, nitrate ion and perchlorate ion.

[0020] In some preferred embodiments of the present invention, the C 1～4 The alkyl group is selected from at least one of a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group.

[0021] In some embodiments of the present invention, the substituents of the substituted aryl are independently selected from at least one of halogen, hydroxyl, aldehyde, acetal, ester, carbonyl, amide, cyano, substituted or unsubstituted fatty alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl; preferably, the heterocycle of the substituted or unsubstituted heterocycloalkyl is selected from at least one of substituted or unsubstituted thiophene and substituted or unsubstituted pyrrole. Preferably, the aryl in the substituted or unsubstituted aryl is selected from at least one of phenanthrenyl, anthracene, indenyl, naphthalene, hydronaphthalene, benzyl, benzyloxy, and phenyl.

[0022] In some embodiments of the present invention, the substituents in the substituted hydrocarbon group are independently selected from at least one of halogen, hydroxyl, aldehyde, acetal, ester, carbonyl, amide, cyano, substituted or unsubstituted fatty alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl; preferably, the heterocycle of the substituted or unsubstituted heterocycloalkyl is selected from at least one of substituted or unsubstituted thiophene and substituted or unsubstituted pyrrole. Preferably, the aryl in the substituted or unsubstituted aryl is selected from at least one of phenanthrenyl, anthracene, indenyl, naphthalene, hydronaphthalene, benzyl, benzyloxy, and phenyl.

[0023] In some embodiments of the present invention, the substituted or unsubstituted hydrocarbon group is selected from substituted or unsubstituted C 1～20 Fatty alkyl, substituted or unsubstituted C 3～20 At least one of cycloalkyl; preferably, the substituent of the substituted hydrocarbon group is selected from C 1～6 Alkoxycarbonyl, C 1～6 Alkoxycarbonylamino, C 1～6 Alkyl, C 1～6 Ester group, hydroxyl group, phenylphosphoryl group, phenyl group, substituted phenyl group, benzyloxycarbonyl group, benzyloxycarbonylamino group, halogen group, phenyl C 1～6 Acyl, substituted phenyl C 1～6 At least one of acyl, N-phthalimide, substituted phenoxy; preferably, the substituted or unsubstituted C 1～20 The fatty alkyl group is selected from substituted or unsubstituted C 1～10 Fatty alkyl; More preferably, the substituted C 1～10 The substituents of the fatty alkyl group are selected from phenylphosphoryl, phenyl, substituted phenyl, benzyloxycarbonyl, benzyloxycarbonylamino, halogen, phenyl C 1～6 Acyl, substituted phenyl C 1～6 At least one of acyl, N-phthalimide, substituted phenoxy; preferably, the substituted or unsubstituted C 3～20 Cycloalkyl is selected from substituted or unsubstituted C3～10 More preferably, the substituted C 3～10 The substituents of the cycloalkyl group are selected from C 1～6 Alkoxycarbonyl, C 1～6 Alkoxycarbonylamino, C 1～6 Alkyl, C 1～6 At least one of an ester group, a hydroxyl group, and a phenylphosphoryl group.

[0024] In some embodiments of the present invention, the C 1～4 The alkyl group is selected from at least one of a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group.

[0025] In some embodiments of the present invention, the compound of formula (I) is selected from phenylacetylene, 4-methylphenylacetylene, 4-methoxyphenylacetylene, 4-tert-butylphenylacetylene, 4-acetamidophenylacetylene, 4-acetoxyphenylacetylene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, 4-bromophenylacetylene, 3-methylphenylacetylene, 3-methoxyphenylacetylene, 3-bromophenylacetylene, 2-methylphenylacetylene, 2-isopropylphenylacetylene, 2-methylphenylacetylene, At least one of oxyphenylacetylene, 2-fluorophenylacetylene, 2-chlorophenylacetylene, 2-bromophenylacetylene, 2-ethynylthiophene, 3-ethynylthiophene, 2,6-diisopropylphenylacetylene, 1,4-diethynylbenzene, 4-formylphenylacetylene, 2-fluoro-6-methoxyphenylacetylene, 9-ethynylphenanthrene, 2,6-dimethoxyphenylacetylene, 2,4,6-trimethylphenylacetylene, and 4-methoxy-3-methoxyacylphenylacetylene.

[0026] In some embodiments of the present invention, the cobalt catalyst is selected from divalent cobalt compounds; preferably, the divalent cobalt compound is selected from at least one of cobalt (II) acetylacetonate, bis(triphenylphosphine)cobalt dichloride, diiodocarbonylcyclopentadienyl cobalt, bis(hexafluoroacetylacetonate)cobalt (II), cobalt (II) metaaluminate, cobalt (II) chlorate, cobalt (II) perchlorate, cobalt (II) fluoride, cobalt (II) hydroxide, cobalt (II) gluconate hydrate, cobalt bis(trifluoromethylsulfonyl)imide, cobalt (II) chloride, cobalt (II) iodide, cobalt (II) trifluoromethanesulfonate, cobalt (II) tetrafluoroborate, cobalt (II) hexafluorophosphate, cobalt (II) sulfate, cobalt (II) nitrate, cobalt (II) acetate, cobalt (II) trifluoroacetate, cobalt (II) citrate, cobalt (II) oxalate, cobalt (II) acrylate, bis(2,2,6,6-tetramethyl-3,5-heptanedione)cobalt (II) and / or their hydrates.

[0027] In some embodiments of the present invention, the boron reagent is selected from 4,4,5,5-tetramethyl-1,3,2-dioxaborolane.

[0028] In some embodiments of the present invention, the base is selected from at least one of an organic base and an inorganic base; preferably, the organic base is selected from a nitrogen-containing organic system having a lone pair of electrons; preferably, the nitrogen-containing organic system having a lone pair of electrons is selected from at least one of an alkylamine and a nitrogen-substituted aromatic heterocycle; more preferably, the alkylamine is selected from at least one of triethylamine, tri-n-butylamine, diethylamine, morpholine, N-methylmorpholine, N-ethylmorpholine, cyclohexylamine, diisopropylamine, triethylenediamine, tetramethylguanidine, N,N-diisopropylethylamine, 1,8-diazobispiro[5.4.0]undec-7-ene, and 1,4-diazabicyclo[2.2.2]octane; preferably, the nitrogen-substituted aromatic heterocycle is selected from at least one of pyridine, 4-dimethylaminopyridine, 2-dimethylaminopyridine, 2-methylpyridine, 2-methoxypyridine, 2-methylpyridine, 2-picolinic acid, 2,6-lutidine, 2,6 -di-tert-butylpyridine, 2-methoxy-6-methylpyridine, 2,6-dimethoxypyridine, 2,6-diaminopyridine, 2,4,6-trimethylpyridine, 2,6-di-tert-butyl-4-methylpyridine, 2,4,6-trifluoropyridine, 2,4,6-trichloropyridine, 2,4,6-tris(trifluoromethyl)pyridine, isoquinoline, quinoline, 2-methylquinoline, quinine at least one; preferably, the inorganic base is selected from lithium carbonate, sodium carbonate , potassium carbonate, cesium carbonate, sodium bicarbonate, , potassium bicarbonate, cesium bicarbonate, ammonium bicarbonate, lithium phosphate, sodium phosphate, potassium phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate, potassium monohydrogen phosphate, potassium dihydrogen phosphate, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium ethoxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, sodium acetate, potassium acetate, sodium formate, sodium trifluoroacetate, sodium benzoate, potassium benzoate.

[0029] In some embodiments of the present invention, the reaction temperature is -78 to 300°C, for example: -78°C, -50°C, -30°C, -20°C, -10°C, -5°C, 0°C, 10°C, 20°C, 25°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 150°C, 200°C, 250°C, 300°C; preferably, the reaction temperature is -50 to 200°C; preferably, the reaction temperature is -30 to 200°C; preferably, the reaction temperature is -10 to 150°C; preferably, the reaction temperature is 0 to 100°C. Depending on the activity of the reaction substrate, the reaction of the present invention can be carried out in a wide temperature range, and can be carried out under freezing conditions, room temperature or heating conditions.

[0030] In some embodiments of the present invention, the solvent is selected from at least one of DMF, THF, DMSO, DMAc, and TOL; preferably, the solvent is selected from DMF.

[0031] In some embodiments of the present invention, the amount of the cobalt catalyst is 0.1% to 10% of the compound of formula (I) in moles, for example: 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 10%; the amount of the cobalt catalyst is 0.1% to 10% of the compound of formula (I) in moles; preferably, the amount of the cobalt catalyst is 0.1% to 5% of the compound of formula (I) in moles; preferably, the amount of the cobalt catalyst is 0.2% to 1% of the compound of formula (I) in moles; more preferably, the amount of the cobalt catalyst is 0.5% of the compound of formula (I) in moles.

[0032] In some embodiments of the present invention, the amount of the ligand is 0.14% to 14% of the compound of formula (I) in moles, for example: 0.14%, 0.28%, 0.7%, 1.4%, 2.8%, 4.2%, 5.6%, 7%, 14%; preferably, the amount of the ligand is 0.14% to 7% of the compound of formula (I); preferably, the amount of the ligand is 0.28% to 1.4% of the compound of formula (I) in moles; more preferably, the amount of the ligand is 0.7% of the compound of formula (I) in moles.

[0033] In some embodiments of the present invention, the ratio of the cobalt catalyst to the ligand is 1:0.5 to 1.6 in moles; preferably, the ratio of the cobalt catalyst to the ligand is 1:1.3 to 1.5; more preferably, the ratio of the cobalt catalyst to the ligand is 1:1.4; for example, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6.

[0034] In some embodiments of the present invention, the amount of the boron reagent is 1-3 equivalents of the compound of formula (I) in moles, for example: 1, 1.1, 1.2, 1.3, 1.4, 1.5, 2, 2.5, 3 equivalents; preferably, the amount of the boron reagent is 1 to 2 equivalents of the compound of formula (I) in moles; preferably, the amount of the boron reagent is 1.2 to 1.5 equivalents of the compound of formula (I) in moles; preferably, the amount of the boron reagent is 1.3 equivalents of the compound of formula (I) in moles.

[0035] In some embodiments of the present invention, the amount of the base used is 3-5 equivalents of the ligand, for example, 3, 3.5, 4, 4.5, or 5 equivalents, measured in moles. Preferably, the amount of the base used is 4 equivalents of the ligand, measured in moles.

[0036] In some embodiments of the present invention, the amount of the solvent used is 0.125 to 1 mol / L of the compound of formula (I).

[0037] In some preferred embodiments of the present invention, the amount of the solvent used is 0.8 mol / L of the compound of formula (I).

[0038] In some embodiments of the present invention, the inert atmosphere is a nitrogen or argon atmosphere.

[0039] In some embodiments of the present invention, the reaction time is 0.1h to 48h, for example: 0.1h, 0.2h, 0.5h, 1h, 1.5h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 15h, 20h, 24h, 30h, 35h, 40h, 45h, 48h; preferably, the reaction time is 0.1h to 24h; preferably, the reaction time is 0.5h to 12h; preferably, the reaction time is 0.5 to 8h; preferably, the reaction time is 0.5 to 4h. The reaction time will vary depending on the reaction scale, the reaction temperature, and the ratio of the reaction raw materials.

[0040] In some embodiments of the present invention, the method further comprises separating and purifying the alkenyl borate obtained by the reaction to obtain a final product; preferably, the specific operation of the separation and purification is selected from at least one of extraction, column chromatography, distillation, decantation, filtration, centrifugation, washing, evaporation, stripping, and adsorption; more preferably, the specific operation of the separation and purification is separation and purification by extraction and column chromatography.

[0041] In some preferred embodiments of the present invention, the specific operation of separation and purification by extraction and column chromatography is to use ethyl acetate and water to extract and wash away the DMF solvent, concentrate, and subject the concentrated residue to column chromatography.

[0042] In some preferred embodiments of the present invention, the eluent for column chromatography is selected from at least one of dichloromethane, n-hexane, ethyl acetate, n-pentane, methanol, and petroleum ether; preferably, the eluent for column chromatography is at least one of n-hexane-ethyl acetate, dichloromethane-methanol, and petroleum ether-ethyl acetate; preferably, the volume ratio of n-hexane to ethyl acetate is 5 to 100:1, for example: 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1; preferably, the volume ratio of dichloromethane to methanol is 20 to 80:1. For example: 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1; preferably, the volume ratio of dichloromethane to methanol is 30-60:1; preferably, the volume ratio of petroleum ether to ethyl acetate is 10-200:1, for example: 10:1, 20:1, 30:1, 40:1, 50:1, 80:1, 100:1, 200:1.

[0043] In some preferred embodiments of the present invention, the column for column chromatography is a silica gel column; preferably, the silica gel of the silica gel column is 300-400 mesh silica gel.

[0044] Another object of the present invention is to provide an alkenyl borate ester, which is prepared by the above method.

[0045] Compared with the prior art, the present invention has the following beneficial effects:

[0046] (1) The cobalt catalyst used in the present invention is abundant in reserves, cheap, readily available, and environmentally friendly; the reaction conditions are mild and highly efficient and selective; the reaction substrate has high tolerance for functional groups and a wide range of substrate sources. In addition to aromatic alkynes, aliphatic alkynes and sterically hindered alkynes can also be used; the reaction can be scaled up to gram levels for preparation; the product has high yield, selectivity, and purity.

[0047] (2) The present invention uses cheap and readily available alkynes as reaction raw materials. In an inert gas reaction atmosphere, a hydroboration reaction occurs under the joint promotion of a cobalt catalyst, a ligand, a base, and a boron reagent to obtain the corresponding alkenyl borate. The reaction has the advantages of low cost, mild conditions, high yield and selectivity, and provides a new synthetic route and method for alkenyl borate, which can provide structurally diverse alkenyl borate for the synthesis of drugs and reagents. DETAILED DESCRIPTION

[0048] The following will clearly and completely describe the concept of the present invention and the technical effects produced in conjunction with the embodiments, so as to fully understand the purpose, characteristics and effects of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention. The test methods used in the embodiments are all conventional methods unless otherwise specified; the materials, reagents, etc. used, unless otherwise specified, can all be reagents and materials obtained from commercial channels.

[0049] In the description of the present invention, reference to terms such as "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples" means that the specific features, structures, materials, or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the exemplary expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0050] Example 1

[0051] This embodiment provides (Z)-styrene pinacol borate, and the specific process is:

[0052]

[0053] Under an inert gas atmosphere, phenylacetylene (0.4 mmol, 1 equiv), cobalt (II) acetylacetonate (0.0004 mmol, 0.001 equiv), ligand L (0.00056 mmol, 1.4 equivalents relative to the cobalt catalyst), 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.52 mmol, 1.3 equiv), and potassium tert-butoxide (0.0022 mmol, 4 equivalents relative to the ligand) were added to a 5 mL reaction bottle, anhydrous DMF (0.5 ml) was added, and the reaction was stirred at room temperature (20 ° C) for 10 min. After the reaction, water and ethyl acetate were added for extraction. The organic phase was collected and dried over anhydrous sodium sulfate, filtered and the solvent was dried, and the product was separated by column chromatography (eluent: petroleum ether, ethyl acetate). The product was a light yellow oily liquid with a yield of 90% and Z:E=98:2;

[0054] The NMR spectrum data of the obtained product are as follows:

[0055] 1H-NMR (400MHz, Chloroform-d) δ7.57(d,J=8.7Hz,2H),7.18(d,J=14.9Hz,1H),6.86(d,J=8.8Hz,2H),5.48(d,J=14.9Hz,1H),3.84(s,3H),1.33(s,12H).

[0056] Example 2

[0057] This embodiment provides (Z)-4-methoxy-styrene pinacol borate, and the specific process is:

[0058]

[0059] The synthesis method of this example differs from that of Example 1 in that phenylacetylene is replaced with an equal molar amount of 4-methoxyphenylacetylene and the reaction is carried out for 3 h. Other operations are the same as those of Example 1. The product of this example is a colorless oily liquid with a yield of 99% and a Z:E ratio of 99:1.

[0060] The NMR spectrum data of the obtained product are as follows:

[0061] 1 H-NMR (400MHz, Chloroform-d) δ7.57(d,J=8.7Hz,2H),7.18(d,J=14.9Hz,1H),6.86(d,J=8.8Hz,2H),5.48(d,J=14.9Hz,1H),3.84(s,3H),1.33(s,12H).

[0062] Example 3

[0063] This embodiment provides (Z)-4-methyl-styrene pinacol borate, and the specific process is:

[0064]

[0065] The synthesis method of this example differs from that of Example 1 in that phenylacetylene was replaced with an equal molar amount of 4-methylphenylacetylene, the amount of cobalt catalyst was increased to 0.004 mmol, and the reaction was carried out for 12 hours. Other operations were the same as those of Example 1. The product of this example was a yellow oily liquid with a yield of 90% and a Z:E ratio of 99:1.

[0066] The NMR spectrum data of the obtained product are as follows:

[0067] 1H-NMR (400MHz, Chloroform-d) δ7.46(d,J=7.6Hz,2H),7.19(d,J=14.9Hz,1H),7.12(d,J=7.7Hz,2H),5.53(d,J=14.9Hz,1H),2.35(s,3H),1.31(s,12H).

[0068] Example 4

[0069] This embodiment provides (Z)-4-methyl-styrene pinacol borate, and the specific process is:

[0070]

[0071] The synthesis method of this example differs from that of Example 1 in that phenylacetylene is replaced with an equal molar amount of 4-tert-butylphenylacetylene, the amount of cobalt catalyst is increased to 0.004 mmol, and the reaction is carried out for 12 hours. Other operations are the same as those of Example 1. The product of this example is a yellow oily liquid with an 82% yield and a Z:E ratio of 99:1.

[0072] The NMR spectrum data of the obtained product are as follows:

[0073] 1 H-NMR (400MHz, Chl-oroform-d) δ7.54(d,J=8.1Hz,2H),7.36(s,2H),7.20(d,J=14.9Hz,1H),5.55(d,J=14.9Hz,1H),1.34(s,9H),1.33(s,12H).

[0074] Example 5

[0075] This embodiment provides (Z)-4-acetamido-styrene pinacol borate, and the specific process is:

[0076]

[0077] The synthesis method of this example differs from that of Example 1 in that phenylacetylene is replaced with an equal molar amount of 4-acetamido-phenylacetylene, the amount of cobalt catalyst is increased to 0.002 mmol, and the reaction is carried out for 10 minutes. Other operations are the same as those of Example 1. The product of this example is a white solid with an 87% yield and a Z:E ratio of 97:3.

[0078] The NMR spectrum data of the obtained product are as follows:

[0079] 1H-NMR(400MHz,Chloroform-d)δ7.53(d,J=8.6Hz,2H),7.45(d,J=8.6Hz,2H),7.30 (s,1H),7.14(d,J=14.9Hz,1H),5.52(d,J=14.9Hz,1H),2.17(s,3H),1.29(s,12H).

[0080] 13 C-NMR (101MHz, CDCl3) δ168.2,147.7,137.8,134.5,129.6,119.0,83.6,24.8,24.8.

[0081] Example 6

[0082] This embodiment provides (Z)-4-fluoro-styrene pinacol borate, and the specific process is:

[0083]

[0084] The synthesis method of this example differs from that of Example 1 in that phenylacetylene was replaced with an equal molar amount of 4-fluoro-phenylacetylene, the amount of cobalt catalyst was increased to 0.004 mmol, and the reaction was carried out for 10 minutes. Other operations were the same as in Example 1. The product of this example was a colorless oily liquid with a yield of 67% and a Z:E ratio of 96:4.

[0085] The NMR spectrum data of the obtained product are as follows:

[0086] 1 H-NMR (400MHz, Chloroform-d) δ7.60-7.49(m,2H),7.17(d,J=14.8Hz,1H),6.99(t,J=8.8Hz,2H),5.56(d,J=14.9Hz,1H),1.29(s,12H).

[0087] Example 7

[0088] This embodiment provides (Z)-4-acetoxy-styrene pinacol borate, and the specific process is:

[0089]

[0090] The synthesis method of this example differs from that of Example 1 in that phenylacetylene was replaced with an equal molar amount of 4-acetoxy-phenylacetylene, the amount of cobalt catalyst was increased to 0.002 mmol, and the reaction was carried out for 10 minutes. Other procedures were the same as in Example 1. The product of this example was a white solid with an 88% yield and a Z:E ratio greater than 99:1.

[0091] The NMR spectrum and high-resolution spectrum data of the obtained product are as follows:

[0092] 1 H-NMR (400MHz, Chloroform-d) δ7.58(d,J=8.5Hz,2H),7.18(d,J=14.9Hz,1H),7.03(d,J=8.6Hz,2H),5.58(d,J=14.9Hz,1H),2.29(s,3H),1.28(s,12H).

[0093] 13 C-NMR (101MHz, CDCl3) δ169.4,150.4,147.3,136.2,129.8,121.0,83.6,24.8,21.2.

[0094] 11 B-NMR (193MHz,CDCl3)δ30.2.

[0095] HRMS(ESI+)m / z calculated for C 16 H 22 BO 4+ ([M+H]+)289.1606; found 289.1603.

[0096] Example 8

[0097] This embodiment provides (Z)-4-chloro-styrene pinacol borate, and the specific process is:

[0098]

[0099] The synthesis method of this example differs from that of Example 1 in that phenylacetylene is replaced with an equal molar amount of 4-chloro-phenylacetylene, the amount of cobalt catalyst is increased to 0.02 mmol, and the amount of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane is increased to 2 equivalents of 4-chloro-phenylacetylene. The reaction is carried out for 24 hours. All other procedures are the same as those of Example 1. The product of this example is a colorless oily liquid with a yield of 74% and a Z:E ratio of 99:1.

[0100] The NMR spectrum data of the obtained product are as follows:

[0101] 1 H-NMR (400MHz, Chloroform-d) δ7.49(d,J=8.5Hz,2H),7.27(d,J=8.5Hz,2H),7.15(d,J=14.8Hz,1H),5.61(d,J=14.9Hz,1H),1.29(s,12H).

[0102] Example 9

[0103] This embodiment provides (Z)-4-bromo-styrene pinacol borate, the specific process is:

[0104]

[0105] The synthesis method of this example differs from that of Example 1 in that phenylacetylene is replaced with an equal molar amount of 4-bromo-phenylacetylene, the amount of cobalt catalyst is increased to 0.02 mmol, the amount of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane is increased to 2 equivalents of 4-bromo-phenylacetylene, and the reaction is carried out for 12 hours. All other procedures are the same as those of Example 1. The product of this example is a yellow oily liquid with a yield of 58% and a Z:E ratio of 99:1.

[0106] The NMR spectrum data of the obtained product are as follows:

[0107] 1 H-NMR (400MHz, Chloroform-d) δ7.42 (s, 4H), 7.13 (d, J = 14.8Hz, 1H), 5.62 (d, J = 14.9Hz, 1H), 1.29 (s, 12H).

[0108] Example 10

[0109] This embodiment provides (Z)-3-methyl-styrene pinacol borate, and the specific process is:

[0110]

[0111] The synthesis method of this example differs from that of Example 1 in that phenylacetylene is replaced with an equal molar amount of 3-methyl-phenylacetylene, the amount of cobalt catalyst is increased to 0.0008 mmol, and the reaction is carried out for 12 hours. Other operations are the same as those of Example 1. The product of this example is a colorless oily liquid with an 80% yield and a Z:E ratio greater than 99:1.

[0112] The NMR spectrum data of the obtained product are as follows:

[0113] 1 H-NMR (400MHz, Chloroform-d) δ7.31 (s, 1H), 7.22 (d, J = 7.4Hz, 1H), 7.15-7.06 (m,2H),7.04-6.96(m,1H),5.49(d,J=14.8Hz,1H),2.26(s,3H),1.21(s,12H).

[0114] Example 11

[0115] This embodiment provides (Z)-3-methoxy-styrene pinacol borate, and the specific process is:

[0116]

[0117] The synthesis method of this example differs from that of Example 1 in that phenylacetylene was replaced with an equal molar amount of 3-methoxy-phenylacetylene, the amount of cobalt catalyst was increased to 0.004 mmol, and the amount of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane was increased to 2 equivalents of 3-methoxy-phenylacetylene. The reaction was carried out for 12 hours. All other procedures were the same as in Example 1. The product of this example was a light yellow oily liquid with a yield of 91% and a Z:E ratio of 97:3.

[0118] The NMR spectrum data of the obtained product are as follows:

[0119] 1 H-NMR(400MHz,Chloroform-d)δ7.25(s,1H),7.14-7.05(m,2H),6.96(d,J=7.5H z,1H),6.73(d,J=8.1Hz,1H),5.50(d,J=15.0Hz,1H),3.72(s,3H),1.19(s,12H).

[0120] Example 12

[0121] This embodiment provides (Z)-3-bromo-styrene pinacol borate, and the specific process is:

[0122]

[0123] The synthesis method of this example differs from that of Example 1 in that phenylacetylene was replaced with an equal molar amount of 3-bromo-phenylacetylene, the amount of cobalt catalyst was increased to 0.004 mmol, and the amount of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane was increased to 2 equivalents of 3-bromo-phenylacetylene. The reaction was continued for 24 hours. All other procedures were the same as in Example 1. The product of this example was a pale yellow oily liquid with a yield of 61% and a Z:E ratio of 99:1.

[0124] The NMR spectrum data of the obtained product are as follows:

[0125] 1 H-NMR (400MHz, Chloroform-d) δ7.82(s,1H),7.37(dd,J=12.8,7.9Hz,2H),7.21-7.09(m,2H),5.66(d,J=14.8Hz,1H),1.31(s,12H).

[0126] Example 13

[0127] This embodiment provides (Z)-2-methyl-styrene pinacol borate, and the specific process is:

[0128]

[0129] The synthesis method of this example differs from that of Example 1 in that phenylacetylene was replaced with an equal molar amount of 2-methyl-phenylacetylene, the amount of cobalt catalyst was increased to 0.0008 mmol, and the reaction was carried out for 12 hours. Other operations were the same as in Example 1. The product of this example was a light yellow oily liquid with a yield of 74% and a Z:E ratio greater than 99:1.

[0130] The NMR spectrum data of the obtained product are as follows:

[0131] 1 H-NMR (400MHz, Chloroform-d) δ7.46-7.33(m,2H),7.23-7.09(m,3H),5.72-5.67(d,J=14.8,1H),2.33(s,3H),1.24(s,12H).

[0132] Example 14

[0133] This embodiment provides (Z)-2-isopropyl-styrene pinacol borate, and the specific process is:

[0134]

[0135] The synthesis method of this example differs from that of Example 1 in that phenylacetylene is replaced with an equal molar amount of 2-isopropylphenylacetylene, the amount of cobalt catalyst is increased to 0.002 mmol, and the reaction is carried out for 0.5 h. All other procedures are the same as those of Example 1. The product of this example is a light yellow oily liquid with an 83% yield and a Z:E ratio greater than 99:1.

[0136] The NMR spectrum and high-resolution spectrum data of the obtained product are as follows:

[0137] 1 H-NMR(400MHz,Chloroform-d)δ7.49(d,J=14.4Hz,1H),7.30(d,J=7.9Hz,1H),7.26-7.21(m,2H),7.1 1-7.04(m,1H),5.66(d,J=14.4Hz,1H),3.15(hept,J=6.9Hz,1H),1.21(d,J=6.9Hz,6H),1.17(s,12H).

[0138] 13C-NMR (101MHz, CDCl3) δ147.4,146.2,137.4,129.3,128.1,124.9,124.2,83.2,29.7,24.7,23.3.

[0139] 11 B-NMR (128 MHz, CDCl3) δ 30.6.

[0140] HRMS(ESI+)m / z calculated for C 17 H 26 BO 2+ ([M+H]+)273.2020; found 273.2017.

[0141] Example 15

[0142] This embodiment provides (Z)-2-methoxy-styrene pinacol borate, and the specific process is:

[0143]

[0144] The synthesis method of this example differs from that of Example 1 in that phenylacetylene was replaced with an equal molar amount of 2-methoxy-phenylacetylene, and the reaction was carried out for 12 hours. Other operations were the same as in Example 1. The product of this example was a light yellow oily liquid with an 89% yield and a Z:E ratio of 98:2.

[0145] The NMR spectrum data of the obtained product are as follows:

[0146] 1 H-NMR(400MHz,Chloroform-d)δ7.52(d,J=7.6Hz,1H),7.48(d,J=14.9Hz,1H),7.25(t ,J=7.7Hz,1H),6.90-6.81(m,2H),5.61(d,J=14.7Hz,1H),3.81(s,3H),1.25(s,12H).

[0147] Example 16

[0148] This embodiment provides (Z)-2-fluoro-styrene pinacol borate, and the specific process is:

[0149]

[0150] The synthesis method of this example differs from that of Example 1 in that phenylacetylene was replaced with an equal molar amount of 2-fluoro-phenylacetylene, the amount of cobalt catalyst was increased to 0.004 mmol, and the reaction was carried out for 12 hours. Other operations were the same as in Example 1. The product of this example was a light yellow oily liquid with an 82% yield and a Z:E ratio of 97:3.

[0151] The NMR spectrum data of the obtained product are as follows:

[0152] 1 H-NMR(400MHz,Chloroform-d)δ7.6(td,J=7.7,1.7Hz,1H),7.32(d,J=14.8Hz,1H),7.27- 7.21(m,1H),7.09-7.04(m,1H),7.03-6.97(m,1H),5.74(d,J=14.9Hz,1H),1.27(s,12H).

[0153] 11 B-NMR (128 MHz, CDCl3) δ 30.3.

[0154] HRMS(APCI+)m / z calculated for C 14 H 19 BFO 2+ ([M+H]+)249.1457; found249.1454.

[0155] Example 17

[0156] This embodiment provides (Z)-2-chloro-styrene pinacol borate, and the specific process is:

[0157]

[0158] The synthesis method of this example differs from that of Example 1 in that phenylacetylene is replaced with an equal molar amount of 2-chloro-phenylacetylene, the amount of cobalt catalyst is increased to 0.02 mmol, and the amount of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane is increased to 3 equivalents of 2-chloro-phenylacetylene. The reaction is continued for 24 hours. All other procedures are the same as those of Example 1. The product of this example is a light yellow oily liquid with an 80% yield and a Z:E ratio of 99:1.

[0159] The NMR spectrum data of the obtained product are as follows:

[0160] 1H-NMR (400MHz, Chloroform-d) δ7.56 (dd, J=7.2, 2.0Hz, 1H), 7.44 (d, J=14.6Hz, 1H),7.37-7.31(m,1H),7.24-7.14(m,2H),5.74(d,J=14.6Hz,1H),1.24(s,12H).

[0161] 13 C-NMR (101MHz, CDCl3) δ145.1,136.9,133.6,130.3,129.2,129.1,126.0,83.5,24.8.

[0162] 11 B-NMR (128 MHz, CDCl3) δ 30.2.

[0163] HRMS(APCI+)m / z calculated for C 14 H 19 BClO 2+ ([M+H]+)265.1161; found265.1159.

[0164] Example 18

[0165] This embodiment provides (Z)-2-bromo-styrene pinacol borate, the specific process is:

[0166]

[0167] The synthesis method of this example differs from that of Example 1 in that phenylacetylene is replaced with an equal molar amount of 2-bromo-phenylacetylene, the amount of cobalt catalyst is increased to 0.02 mmol, and the amount of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane is increased to 3 equivalents of 2-bromo-phenylacetylene. The reaction is carried out for 48 hours. All other procedures are the same as those of Example 1. The product of this example is a light yellow oily liquid with an 80% yield and a Z:E ratio of 97:3.

[0168] The NMR spectrum data of the obtained product are as follows:

[0169] 1 H-NMR(400MHz,Chloroform-d)δ7.54(dt,J=7.9,1.4Hz,2H),7.37(d,J=14.5Hz,1H), 7.25-7.20(m,1H),7.13(td,J=7.7,1.7Hz,1H),5.71(d,J=14.6Hz,1H),1.23(s,12H).

[0170] 13 C-NMR (151MHz, CDCl3) δ147.4,138.6,132.3,130.5,129.3,126.6,123.8,83.5,24.8.

[0171] 11 B-NMR (193MHz,CDCl3)δ30.1.

[0172] HRMS(APCI+)m / z calculated for C 14 H 19 BBr1O 2+ ([M+H]+)309.0656; found309.0649.

[0173] Example 19

[0174] This embodiment provides (Z)-2-[thiophen-2-yl]-vinyl pinacol borate, and the specific process is:

[0175]

[0176] The synthesis method of this example differs from that of Example 1 in that phenylacetylene is replaced with an equal molar amount of 2-ethynylthiophene, the amount of cobalt catalyst is increased to 0.002 mmol, and the amount of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane is increased to 2 equivalents of 2-ethynylthiophene. The reaction is carried out for 12 hours. All other procedures are the same as those of Example 1. The product of this example is a pale yellow oily liquid with an 81% yield and a Z:E ratio of 99:1.

[0177] The NMR spectrum data of the obtained product are as follows:

[0178] 1 H-NMR(400MHz,Chloroform-d)δ7.40(d,J=3.6Hz,1H),7.28(d,J=5.0Hz,1H),7.23( d,J=15.0Hz,1H),6.99(dd,J=5.1,3.6Hz,1H),5.44(d,J=15.1Hz,1H),1.34(s,12H).

[0179] Example 20

[0180] This embodiment provides (Z)-2-[thiophen-3-yl]-vinyl pinacol borate, and the specific process is:

[0181]

[0182] The synthesis method of this example differs from that of Example 1 in that phenylacetylene is replaced with an equal molar amount of 3-ethynylthiophene, the amount of cobalt catalyst is increased to 0.002 mmol, and the reaction is carried out for 12 hours. Other operations are the same as those of Example 1. The product of this example is a light yellow oily liquid with a yield of 93% and a Z:E ratio greater than 99:1.

[0183] The NMR spectrum data of the obtained product are as follows:

[0184] 1 H-NMR (400MHz, Chloroform-d) δ7.62(dd,J=38.7,3.8Hz,2H),7.23(dd,J=5.0,3.0Hz,1H),7.17(d,J=15.1Hz,1H),5.48(d,J=15.1Hz,1H),1.32(s,12H).

[0185] Example 21

[0186] This embodiment provides (Z)-2,6-diisopropyl-styrene pinacol borate, and the specific process is:

[0187]

[0188] The synthesis method of this example differs from that of Example 1 in that phenylacetylene is replaced with an equal molar amount of 2,6-diisopropylphenylacetylene, the amount of cobalt catalyst is increased to 0.002 mmol, and the reaction is carried out for 12 hours. Other operations are the same as those of Example 1. The product of this example is a light yellow oily liquid with a yield of 98% and a Z:E ratio greater than 99:1.

[0189] The NMR spectrum data of the obtained product are as follows:

[0190] 1 H-NMR(400MHz,Chloroform-d)δ7.36(d,J=14.5Hz,1H),7.25–

[0191] 7.18(m,1H),7.09(d,J=7.7Hz,2H),5.91(d,J=14.5Hz,1H),3.19(hept,J=6.9Hz,2H),1.17(d,J=6.5Hz,12H),1.05(s,12H).

[0192] 13 C-NMR (101MHz, CDCl3) δ148.6,145.6,137.1,126.9,121.6,82.8,30.0,24.6,23.4.

[0193] 11B-NMR (128MHz,CDCl3)δ29.6.

[0194] Example 22

[0195] This embodiment provides (Z)-2-methoxy, 6-fluoro-styrene pinacol borate, the specific process is:

[0196]

[0197] The synthesis method of this example differs from that of Example 1 in that phenylacetylene is replaced with an equal molar amount of 2-methoxy-6-fluoro-phenylacetylene, the amount of cobalt catalyst is increased to 0.002 mmol, and the reaction is carried out for 12 hours. Other procedures are the same as those of Example 1. The product of this example is a white solid with an 88% yield and a Z:E ratio of 99:1.

[0198] The NMR spectrum data of the obtained product are as follows:

[0199] 1 H-NMR(600MHz,Chloroform-d)δ7.16(q,J=8.0Hz,1H),7.04(d,J=14.8Hz,1H),6.68–

[0200] 6.61(m,2H),5.88(d,J=14.8Hz,1H),3.81(s,3H),1.21(s,12H).

[0201] 13 C-NMR (151MHz, CDCl3) δ161.1,159.5,158.2,136.3,128.7,128.6,116.6,116.5,107.9,107.8,106.0,106.0,83.1,56.0,24.8.

[0202] 11 B-NMR (193MHz,CDCl3)δ29.6.

[0203] 19 F-NMR (565MHz,CDCl3)δ-113.4.

[0204] HRMS(ESI+)m / z calculated for C 15 H 21 BFO 3+ ([M+H]+)279.1562; found279.1565.

[0205] Example 23

[0206] This embodiment provides (Z)-9-phenanthrenyl pinacol borate, and the specific process is:

[0207]

[0208] The synthesis method of this example differs from that of Example 1 in that phenylacetylene was replaced with an equal molar amount of 9-ethynylphenanthrene, the amount of cobalt catalyst was increased to 0.004 mmol, and the reaction was carried out for 12 h. Other operations were the same as those of Example 1. The product of this example was a white solid with an 82% yield and a Z:E ratio of 98:2.

[0209] The NMR spectrum data of the obtained product are as follows:

[0210] 1 H-NMR(600MHz,Chloroform-d)δ8.73(d,J=8.1Hz,1H),8.68(d,J=8.1Hz,1H),8.11 (d,J=8.0Hz,1H),7.91(d,J=14.2Hz,1H),7.87(d,J=7.7Hz,1H),7.84(s,1H),7.69–

[0211] 7.60(m,4H),5.98(d,J=14.2Hz,1H),1.18(s,12H).

[0212] 13 C-NMR (151MHz, CDCl3) δ146.5,135.0,131.5,130.9,130.5,130.2,128.6,127.1,126.6,126.6,126.5,126.3,125.4,122.9,122.6,83.3,24.7.

[0213] 11 B-NMR (193MHz,CDCl3)δ30.6.

[0214] HRMS(ESI+)m / z calculated for C 22 H 24 BO 2+ ([M+H]+)338.1864; found 331.1862.

[0215] Example 24

[0216] This embodiment provides (Z)-2,6-dimethoxy-styrene pinacol borate, and the specific process is:

[0217]

[0218] The synthesis method of this example differs from that of Example 1 in that phenylacetylene is replaced with an equal molar amount of 2,6-dimethoxyphenylacetylene, the amount of cobalt catalyst is increased to 0.002 mmol, and the reaction is carried out for 1 hour. Other operations are the same as those of Example 1. The product of this example is a white solid with a yield of 90% and a Z:E ratio of >99:1.

[0219] The NMR spectrum data of the obtained product are as follows:

[0220] 1 H-NMR (400MHz, Chloroform-d) δ7.16(t,J=8.3Hz,1H),7.06(d,J=14.8Hz,1H),6.53(d,J=8.3Hz,2H),5.84(d,J=14.8Hz,1H),3.77(s,6H),1.18(s,12H).

[0221] Example 25

[0222] This embodiment provides (Z)-2,4,6-trimethyl-styrene pinacol borate, and the specific process is:

[0223]

[0224] The synthesis method of this example differs from that of Example 1 in that phenylacetylene was replaced with an equal molar amount of 2,4,6-trimethylphenylacetylene, the amount of cobalt catalyst was increased to 0.002 mmol, and the reaction was carried out for 12 hours. Other operations were the same as those of Example 1. The product of this example was a white solid with a yield of 90% and a Z:E ratio of 98:2.

[0225] The NMR spectrum data of the obtained product are as follows:

[0226] 1 H-NMR (600MHz, Chloroform-d) δ7.17(d,J=14.5Hz,1H),6.81(s,2H),5.84(d,J=14.5Hz,1H),2.28(s,3H),2.20(s,6H),1.08(s,12H).

[0227] 13 C-NMR (151MHz, CDCl3) δ148.4,136.4,135.7,135.1,127.4,82.8,24.6,21.0,20.5.

[0228] 11 B-NMR (128MHz,CDCl3)δ28.8.

[0229] HRMS(ESI+)m / z calculated for C 17 H 26 B1O 2+ ([M+H]+)273.2020; found273.2018.

[0230] Example 26

[0231] This embodiment provides (Z,Z)-1,4-bisvinylpinacol borate benzene, and the specific process is:

[0232]

[0233] The synthesis method of this example differs from that of Example 1 in that phenylacetylene is replaced with 0.2 mmol of 1,4-diethynylbenzene, the amount of cobalt catalyst is increased to 0.002 mmol, and the amount of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane is increased to 3 equivalents of 1,4-diethynylbenzene. The reaction is carried out for 1 hour. Other operations are the same as those of Example 1. The product of this example is a white solid with an 82% yield and a Z:E ratio of 95:5.

[0234] The NMR spectrum data of the obtained product are as follows:

[0235] 1 H-NMR (400MHz, Chloroform-d) δ7.51 (s, 4H), 7.18 (d, J = 14.9Hz, 2H), 5.58 (d, J = 14.9Hz, 2H), 1.30 (s, 24H).

[0236] Example 27

[0237] This embodiment provides (Z)-1-pinacol borate-1-octene, and the specific process is:

[0238]

[0239] The synthesis method of this example differs from that of Example 1 in that an equal molar amount of 1-octyne is replaced by phenylacetylene, the amount of cobalt catalyst is increased to 0.004 mmol, and the reaction is carried out for 24 hours. Other operations are the same as those of Example 1. The product of this example is a colorless oily liquid with a yield of 74% and a Z:E ratio of 98:2.

[0240] The NMR spectrum data of the obtained product are as follows:

[0241] 1H-NMR (400MHz, Chloroform-d) δ6.43 (dt, J=14.3, 7.5Hz, 1H), 5.32 (dt, J=13.5, 1.3Hz, 1H),2.38(qd,J=7.5,1.2Hz,2H),1.41-1.27(m,8H),1.26(s,12H),0.88(t,J=6.8,3H).

[0242] Example 28

[0243] This embodiment provides (Z)-1-pinacol borate-4-nitrile-1-butene, and the specific process is:

[0244]

[0245] The synthesis method of this example differs from that of Example 1 in that an equal molar amount of 4-nitrile-1-butyne is replaced with phenylacetylene, the amount of cobalt catalyst is increased to 0.004 mmol, and the reaction is carried out for 12 hours. Other operations are the same as those of Example 1. The product of this example is a colorless oily liquid with a yield of 99% and a Z:E ratio greater than 99:1.

[0246] The NMR spectrum data of the obtained product are as follows:

[0247] 1 H-NMR(400MHz,Chloroform-d)δ6.35(dt,J=14.1,7.4Hz,1H),5.45(d,J=13.4Hz,1H ),2.53(q,J=7.3Hz,2H),2.33(t,J=7.3Hz,2H),1.77(p,J=7.2Hz,2H),1.27(s,12H).

[0248] 13 C-NMR (101MHz, CDCl3) δ151.5,119.9,83.2,31.0,25.2,24.9,16.4.

[0249] Example 29

[0250] This embodiment provides (Z)-1-pinacol borate-6-chloro-1-hexene, and the specific process is:

[0251]

[0252] The synthesis method of this example differs from that of Example 1 in that an equal molar amount of 6-chloro-1-hexyne is replaced with phenylacetylene, the amount of cobalt catalyst is increased to 0.004 mmol, and the reaction is carried out for 12 hours. All other procedures are the same as those of Example 1. The product of this example is a colorless oily liquid with a yield of 63% and a Z:E ratio of 95:5. The NMR spectrum data of the obtained product are as follows:

[0253] 1 H-NMR(400MHz,Chloroform-d)δ6.37(dt,J=14.3,7.5Hz,1H),5.34(dt,J=13.5,1.2Hz,1H),3.53(t,J =6.8Hz,2H),2.40(qd,J=7.4,1.2Hz,2H),1.76(p,J=6.9Hz,2H),1.51(p,J=7.3Hz,2H),1.24(s,12H).

[0254] 13 C-NMR (101MHz, CDCl3) δ154.1,82.9,44.9,31.8,31.1,26.5,24.9.

[0255] 11 B-NMR (128 MHz, CDCl3) δ 29.8.

[0256] HRMS(APCI+)m / z calculated for C 12 H 23 BClO 2+ ([M+H]+)245.1474; found245.1470.

[0257] Example 30

[0258] This embodiment provides (Z)-1-pinacol borate-4-phenyl-1-butene, and the specific process is:

[0259]

[0260] The synthesis method of this example differs from that of Example 1 in that phenylacetylene is substituted for an equal molar amount of 4-phenyl-1-butyne, the amount of cobalt catalyst is increased to 0.004 mmol, and the reaction is carried out for 12 hours. Other operations are the same as those of Example 1. The product of this example is a colorless oily liquid with a yield of 60% and a Z:E ratio of 98:2.

[0261] The NMR spectrum data of the obtained product are as follows:

[0262] 1H-NMR (400MHz, Chloroform-d) δ7.34-7.16(m,5H),6.49(dt,J=13.3,6.0Hz,1H),5.39(d,J=13.5Hz,1H),2.81–2.68(m,4H),1.27(s,12H).

[0263] Example 31

[0264] This embodiment provides (Z)-1-pinacol borate-2-cyclopropylethylene, and the specific process is as follows:

[0265]

[0266] The synthesis method of this example differs from that of Example 1 in that an equal molar amount of cyclopropylacetylene is replaced by phenylacetylene, the amount of cobalt catalyst is increased to 0.004 mmol, and the reaction is carried out for 12 hours. Other operations are the same as those of Example 1. The product of this example is a light yellow oily liquid with an 81% yield and a Z:E ratio of 98:2.

[0267] The NMR spectrum data of the obtained product are as follows:

[0268] 1 H-NMR (400MHz, Chloroform-d) δ5.73-5.58(m,1H),5.18(d,J=13.5Hz,1H),2.35-2.23(m,1H),1.27(s,12H),0.87-0.78(m,2H),0.45-0.36(m,2H).

[0269] Example 32

[0270] This embodiment provides (Z)-1-pinacol borate-2-cyclohexylethylene, and the specific process is:

[0271]

[0272] The synthesis method of this example differs from that of Example 1 in that an equal molar amount of cyclohexylacetylene is replaced by phenylacetylene, the amount of cobalt catalyst is increased to 0.004 mmol, and the reaction is carried out for 12 hours. Other operations are the same as those of Example 1. The product of this example is a light yellow oily liquid with a yield of 75% and a Z:E ratio of 97:3.

[0273] The NMR spectrum data of the obtained product are as follows:

[0274] 1H-NMR (400MHz, Chloroform-d) δ6.25 (dd, J=13.3, 9.4Hz, 1H), 5.22 (dd, J=13.5, 0.8Hz, 1H) ,2.78-2.62(m,1H),1.72-1.62(m,4H),1.36-1.27(m,2H),1.26(s,12H),1.23-1.01(m,4H).

[0275] Example 33

[0276] This embodiment provides (Z)-1-pinacol borate-3-[tert-butyldimethylsilyloxy]-propylene, and the specific process is:

[0277]

[0278] The synthesis method of this example differs from that of Example 1 in that an equal molar amount of 3-tert-butyldimethylsilyloxy-1-propyne is replaced with phenylacetylene, the amount of cobalt catalyst is increased to 0.02 mmol, and the amount of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane is increased to 2 equivalents of 3-tert-butyldimethylsilyloxy-1-propyne. The reaction is then allowed to proceed for 12 hours. All other procedures are the same as those of Example 1. The product of this example is a pale yellow oily liquid with a yield of 48% and a Z:E ratio of 97:3.

[0279] The NMR spectrum data of the obtained product are as follows:

[0280] 1 H-NMR (400MHz, Chloroform-d) δ6.50(dt,J=12.9,5.9Hz,1H),5.38(d,J=13.8Hz,1H),4.49(d,J=6.1Hz,2H),1.25(s,12H),0.90(s,9H),0.07(s,6H).

[0281] Examples 34 to 39

[0282] Using 0.002 mmol CoCl2 as a catalyst, 2 ml DMF as a solvent, 0.2 mmol phenylacetylene, 3 equivalents of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 0.008 mmol potassium tert-butoxide, and 0.002 mmol of ligand, different ligands were reacted. The reaction steps were the same as in Example 1. The ligands used and the yields of the corresponding products are shown in Table 1 below.

[0283] Table 1

[0284] serial number ligand Yield of Z-type product (%) Example 34 CNC-H <1 Example 35 CNC-Me <1 Example 36 CNC-Et 5 Example 37 CNC-iPr 30 Example 38 CNC-tBu <1 Example 39 CNC-Mes <1

[0285] The ligand structure is as follows:

[0286]

[0287] As can be seen from Table 1, the structure of the ligand has a very obvious effect on the yield, and moderate steric hindrance of the ligand is more conducive to obtaining Z-type compounds.

[0288] Examples 40 to 44

[0289] Using 0.0016 mmol CNC-iPr as a ligand, 0.0016 mmol CoCl2 as a catalyst, DMF as a solvent, 0.0064 mmol potassium tert-butoxide, 0.4 mmol phenylacetylene as a reaction substrate, and 4,4,5,5-tetramethyl-1,3,2-dioxaborolane as 3 equivalents of phenylacetylene, the reaction was carried out at different phenylacetylene concentrations. The reaction steps were the same as in Example 1, and the yields of the corresponding products at different phenylacetylene concentrations are shown in Table 2 below.

[0290] Table 2

[0291] serial number Phenylacetylene concentration Yield of type E product (%) Yield of Z-type product (%) Example 40 0.05M 0 7 Example 41 0.1M 0 98 Example 42 0.2M 76 24 Example 43 0.3M 76 24 Example 44 0.4M 96 4

[0292] This reaction first generates Z product, and then converts Z product into E product. As can be seen from Table 2, the higher the concentration of phenylacetylene, the stronger the activity of the selective hydroboration reaction. When the concentration is increased to 0.4M, the generated Z type product can be completely converted into E type product. When the concentration is 0.1M, the activity is not enough to promote the conversion of ZE type product.

[0293] Examples 45 to 48

[0294] Using 0.0006 mmol CNC-iPr as a ligand, 0.0006 mmol CoCl2 as a catalyst, 0.5 ml of solvent, 0.0024 mmol potassium tert-butoxide, 0.2 mmol phenylacetylene, and 3 equivalents of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane, the reaction was carried out in different solvents. The reaction steps were the same as in Example 1. The yields of the corresponding products in different solvents are shown in Table 3 below.

[0295] Table 3

[0296] serial number solvent Yield of Z-type product (%) Example 45 DMA 17 Example 46 NMP 13 Example 47 DMSO <1 Example 48 DMF 58

[0297] No E-type product was produced in the above examples.

[0298] As can be seen from Table 3, DMF is used as the reaction solvent and the reaction yield is the highest.

[0299] Examples 49 to 52

[0300] Using 0.0006 mmol CNC-iPr as a ligand, 0.0006 mmol of catalyst, 0.5 ml of DMF as a solvent, 0.0024 mmol of potassium tert-butoxide, 0.2 mmol of phenylacetylene, and 3 equivalents of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane, the reaction was carried out under different catalysts. The reaction steps were the same as in Example 1. The yields of the corresponding products under different catalysts are shown in Table 4 below.

[0301] Table 4

[0302] serial number solvent Yield of type E product (%) Yield of Z-type product (%) Example 49 <![CDATA[CoCl2]]> 0 91 Example 50 <![CDATA[CoBr2]]> 0 35 Example 51 <![CDATA[Co(acac)2]]> 52 46 Example 52 <![CDATA[Co(OAc)2]]> 50 40

[0303] It can be seen from Table 4 that cobalt acetylacetonate has the highest catalytic activity and the highest yield, and more Z is converted into E.

[0304] Examples 53 to 58

[0305] Using CNC-iPr as a ligand, 0.0006 mol Co(acac)2 as a catalyst, 0.5 ml DMF as a solvent, the amount of potassium tert-butoxide is 4 equivalents of the ligand, 0.2 mmol phenylacetylene, and the amount of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane is 3 equivalents of phenylacetylene. The reaction is carried out at different equivalents of the ligand relative to the catalyst. The reaction steps are the same as in Example 1. The yields of the corresponding products at different equivalents of the ligand relative to the catalyst are shown in Table 5 below.

[0306] Table 5

[0307]

[0308]

[0309] It can be seen from Table 5 that too much or too little ligand will affect the reaction yield, and the highest ligand equivalent of the overall reaction product is 1.4 equivalents.

[0310] Example 59

[0311] The practical application value of the reaction was explored using 1.4 equivalents of CNC-iPr as a ligand, 0.15 mmol Co(acac)2 as a catalyst, 37.5 ml of DMF as a solvent, 0.84 mmol of potassium tert-butoxide, 30 mmol of phenylacetylene, and 1.3 equivalents of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane as phenylacetylene. The reaction steps were the same as in Example 1, and the yields of the corresponding products are shown in Table 6 below.

[0312] Table 6

[0313] serial number Reaction time Yield (%) Z / E Example 59 60min 97 97:3

[0314] As can be seen from Table 6, the product can still be obtained with a yield of up to 97% at a reaction scale of 30 mmol phenylacetylene. 6.7 g of liquid product can be obtained by direct extraction and water washing without column chromatography purification.

[0315] Examples 60 to 65

[0316] The amount of CNC-iPr used is 1.4 equivalents of the catalyst, 0.0006 mmol Co(acac)2, 0.25 ml of DMF is used as the solvent, 0.00336 mmol of potassium tert-butoxide, 0.2 mmol of phenylacetylene, and the amount of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane used is 3 equivalents of phenylacetylene. The catalyst, ligand, and base are omitted accordingly. The reaction steps are the same as in Example 1, and the yields of the corresponding products are shown in Table 7 below.

[0317] Table 7

[0318] serial number ligand catalyst alkali Yield (%) Example 60 CNC-iPr <![CDATA[Co(acac)2]]> / No product Example 61 CNC-iPr / tBuOK No product Example 62 / <![CDATA[Co(acac)2]]> tBuOK No product Example 63 CNC-iPr / / No product Example 64 / <![CDATA[Co(acac)2]]> / No product Example 65 / / tBuOK No product

[0319] It can be seen from Table 7 that the reaction requires ligand, metal and base.

[0320] Implementation Examples 66-71

[0321] Using 0.002 mmol CoCl2 as a catalyst, 0.002 mmol of ligand, 0.008 mol of potassium tert-butoxide as a base, 2 ml of DMF as a solvent, 0.4 mmol of phenylacetylene, and 3 equivalents of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane, the reaction was carried out under different ligands. The reaction steps were the same as in Example 1. The yields of the corresponding products under different ligands are shown in Table 8 below.

[0322] Table 8

[0323] serial number ligand Yield (%) Z / E Example 66 CNC-H <1 / Example 67 CNC-Me 71 3:97 Example 68 CNC-Et 78 36:64 Example 69 CNC-iPr 99 2:98 Example 70 CNC-tBu 7 <1:99 Example 71 CNC-Mes <1 /

[0324] It can be seen from Table 8 that compared with the ligands CNC-Me, CNC-Et and CNC-iPr, the product yields are relatively low when the ligands are CNC-Me and CNC-Et, but the catalytic activities of the ligands CNC-Me and CNC-Et are comparable.

[0325] In summary, the nitrogen heterocyclic carbene ligand of the present invention deprotonates under the action of a base to form a carbene-active ligand, which then coordinates with cobalt to produce a cobalt complex. The cobalt complex is reduced with 4,4,5,5-tetramethyl-1,3,2-dioxaborolane to produce a catalytically active cobalt hydrogen intermediate. This cobalt hydrogen species reacts with an alkyne, releasing hydrogen to produce an alkynyl cobalt species. 4,4,5,5-tetramethyl-1,3,2-dioxaborolane reacts with the alkynyl cobalt to produce a pinacol-alkyne-coordinated cobalt hydrogen. This cobalt hydrogen undergoes an in situ insertion reaction to form Z-selective styrene pinacol borate, which simultaneously reacts with another molecule of alkyne to produce the catalytically active cobalt hydrogen intermediate.

[0326] It can be clearly seen from all the above examples that when the method of the present invention is adopted, that is, a reaction system consisting of a cobalt compound as a catalyst (especially cobalt acetylacetonate), a ligand (especially CNC-iPr), a boron reagent (especially pinacol borane), a base (especially potassium tert-butoxide) and a suitable organic solvent (especially DMF), different alkynes can undergo hydroboration to obtain the corresponding alkenyl borate esters, providing a new synthetic route for the efficient and rapid synthesis of alkenyl borate ester compounds.

[0327] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A method for preparing an alkenyl borate, characterized in that: The steps include: In an inert atmosphere, the compound of formula (I) The compound of formula (II) is obtained by reacting with a cobalt catalyst, a ligand, a boron reagent and a base. The reaction is carried out in a solvent; wherein R1 is selected from thiophene, a substituted or unsubstituted aryl group, or a substituted or unsubstituted hydrocarbon group; the substituents in the substituted aryl group are independently selected from at least one of halogen, cyano, aliphatic alkyl, alkoxy, cycloalkyl, and aryl groups; the aryl group in the substituted or unsubstituted aryl group is selected from at least one of phenanthrenyl, anthracenyl, indenyl, naphthyl, hydronaphthyl, and phenyl groups; The hydrocarbon group in the substituted or unsubstituted hydrocarbon group is selected from at least one of a C1-10 fatty alkyl group and a C3-10 cycloalkyl group; the substituent of the substituted hydrocarbon group is selected from at least one of a C1-6 alkyl group, a phenyl group, and a halogen group; Alternatively, the compound of formula (I) is selected from 4-acetoxyphenylacetylene, 1,4-diethynylbenzene, 3-tert-butyldimethylsilyloxy-1-propyne or 4-acetamidophenylacetylene; The solvent is selected from at least one of DMF, THF, DMA and toluene. The ligand includes a cation and an anion, and the cation of the ligand is shown in formula (III): Wherein, R2, R3 are independently selected from C 1~4 alkyl; The anion of the ligand is selected from at least one of halide ion, tetrafluoroborate ion, hexafluorophosphate ion, trifluoromethanesulfonate ion, acetate ion, nitrate ion and perchlorate ion; The cobalt catalyst is selected from divalent cobalt compounds; the divalent cobalt compound is selected from at least one of cobalt (II) acetylacetonate, bis(triphenylphosphine)cobalt dichloride, diiodocarbonylcyclopentadienyl cobalt, bis(hexafluoroacetylacetonate)cobalt (II), cobalt (II) metaaluminate, cobalt (II) chlorate, cobalt (II) perchlorate, cobalt (II) fluoride, cobalt (II) hydroxide, cobalt (II) gluconate hydrate, bis(trifluoromethylsulfonyl)imide cobalt, cobalt (II) chloride, cobalt (II) iodide, cobalt (II) trifluoromethanesulfonate, cobalt (II) tetrafluoroborate, cobalt (II) hexafluorophosphate, cobalt (II) sulfate, cobalt (II) nitrate, cobalt (II) acetate, cobalt (II) trifluoroacetate, cobalt (II) citrate, cobalt (II) oxalate, cobalt (II) acrylate, bis(2,2,6,6-tetramethyl-3,5-heptanedione)cobalt (II) and / or hydrates thereof; The boron reagent is selected from 4,4,5,5-tetramethyl-1,3,2-dioxaborolane; The base is selected from at least one of an organic base and an inorganic base.

2. The method for preparing alkenyl borate according to claim 1, wherein: The compound of formula (I) is at least one selected from phenylacetylene, 4-methylphenylacetylene, 4-methoxyphenylacetylene, 4-tert-butylphenylacetylene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, 4-bromophenylacetylene, 3-methylphenylacetylene, 3-methoxyphenylacetylene, 3-bromophenylacetylene, 2-methylphenylacetylene, 2-isopropylphenylacetylene, 2-methoxyphenylacetylene, 2-fluorophenylacetylene, 2-chlorophenylacetylene, 2-bromophenylacetylene, 2-ethynylthiophene, 3-ethynylthiophene, 2,6-diisopropylphenylacetylene, 2-fluoro-6-methoxyphenylacetylene, 9-ethynylphenanthrene, 2,6-dimethoxyphenylacetylene, and 2,4,6-trimethylphenylacetylene.

3. The method for preparing alkenyl borate according to claim 1, wherein In moles, the amount of the cobalt catalyst is 0.1% to 10% of the compound of formula (I); in moles, the amount of the ligand is 0.14% to 14% of the compound of formula (I); in moles, the amount of the boron reagent is 1 to 3 equivalents of the compound of formula (I); in moles, the amount of the base is 3 to 5 equivalents of the ligand; and the amount of the solvent is 0.125 to 1 mol / L of the compound of formula (I).

4. The method for preparing alkenyl borate according to claim 1, wherein: The reaction temperature is -78 to 300° C.; the reaction time is 0.1 to 48 hours.

5. The method for preparing alkenyl borate according to claim 1, wherein: The method further comprises separating and purifying the compound of formula (II) obtained by the reaction.

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