Preparation method of alkenyl gem-diborate

Abstract

The invention relates to the technical field of organic synthetic chemistry, and discloses a preparation method of alkenyl gem-diborate. According to the preparation method of the alkenyl gem-diborate, a cobalt catalyst serves as a core, a high-activity cobalt complex is formed under the combined action of a specific ionic N-heterocyclic carbene ligand and alkali, the complex can be reduced into a catalytic activity intermediate by a boron test, regeneration of the cobalt catalyst is achieved, and the next round of reaction continues to be catalyzed. The adopted cobalt catalyst is rich in reserves, low in price, easy to obtain and environment-friendly; reaction conditions are mild, and high efficiency and high selectivity are achieved; the reaction substrate functional group tolerance is high, the substrate source is wide, the method is suitable for aromatic alkyne, and aliphatic alkyne and alkyne with large steric hindrance can also be adopted; the reaction can be amplified to a gram scale for preparation; the yield, the selectivity and the purity of the product are improved; the invention provides a new synthesis route and method for alkenyl gem-diborates, and can provide alkenyl gem-diborates with various structures for synthesis of polysubstituted olefins, natural products or pharmaceutical molecules.

Description

Technical Field

[0001] This invention relates to the field of organic synthetic chemistry, and in particular to a method for preparing an alkenyl geminosine diboronic acid ester. Background Technology

[0002] Organoboroesters, with their low toxicity and functional group compatibility, are fundamental materials widely used in organic synthesis. Among them, polyboron compounds have attracted much attention due to their diversity and tunable reactivity. Polyboron compounds have shown great potential in the synthesis of polysubstituted alkenes, natural products, and drug molecules. For example, alkenyl geminoboronates can utilize the difference in reactivity between two adjacent boron substituents to synthesize polysubstituted alkenes with specific stereoconfigurations through stepwise cross-coupling.

[0003] However, the selective synthesis of alkenyl geminoboronates is quite challenging. Traditional methods mainly involve the addition of an stoichiometric amount of triboronylmethyllithium reagent to the carbonyl group, or the preparation of geminoboronates by an stoichiometric reaction of a geminohalogenated olefin, a lithium reagent, and a boron reagent. However, these methods suffer from poor atom economy, high synthesis costs, and are prone to causing significant resource waste and environmental pollution. Therefore, how to achieve a boration method with high efficiency, high selectivity, high atom economy, and broad substrate applicability using inexpensive catalysts has become the focus of current research.

[0004] Existing technology discloses a selective bisboration reaction of alkynes catalyzed by cobalt complexes of radical imine ligands, as shown in Formula I. This method can achieve 1,1-selective bisboration of alkyl and two examples of aryl alkynes to construct alkenyl geminiborates, and for the first time achieves selective bisboration of alkenyl geminiborates using inexpensive cobalt.

[0005]

[0006] Furthermore, existing technologies disclose the use of a base catalyst to achieve the diboration reaction of electron-deficient alkynes, as shown in Formula II. However, this method is only applicable to electron-deficient alkyne substrates and is not suitable for common alkyl alkynes or aryl alkynes, thus limiting its widespread use.

[0007]

[0008] It is evident that although some progress has been made in the 1,1-diboration reaction of alkynes, this reaction usually relies on expensive and complex ligands that require multiple steps of synthesis, or has limitations in substrate applicability, poor compatibility with aryl alkynes, difficulty in handling sterically hindered / aliphatic alkynes, and a significant decrease in yield when the reaction scale is increased, which cannot meet the needs of industrialization and greatly limits its widespread use. Summary of the Invention

[0009] The present invention aims to at least solve one of the aforementioned technical problems existing in the prior art. Therefore, one objective of the present invention is to provide a method for preparing an alkenyl geminitroboronate.

[0010] The second objective of this invention is to provide an alkenyl geminolate.

[0011] A third objective of this invention is to provide applications of alkenyl geminolates.

[0012] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0013] The first aspect of the present invention provides a method for preparing an alkenyl geminolate, comprising the following steps:

[0014] Under an inert atmosphere, compound (a) is made The reaction, under the action of a cobalt catalyst, an ionic nitrogen heterocyclic carbene ligand, a boron reagent, and a base, yields an alkenyl geminoboron ester as shown in formula (A).

[0015] in:

[0016] The cationic moiety of the ionic nitrogen heterocyclic carbene ligand is shown in formula (b):

[0017] The anionic portion of the ionic nitrogen heterocyclic carbene ligand is selected from at least one of halide ions, tetrafluoroborate ions, hexafluorophosphate ions, trifluoromethanesulfonate ions, acetate ions, nitrate ions, and perchlorate ions;

[0018] In formulas (a) and (A), R1 is selected from hydrogen, heterocycles, substituted or unsubstituted aryl groups, and substituted or unsubstituted hydrocarbon groups;

[0019] In equation (b), R2 and R3 are each independently selected from C. 1-4 Alkyl group; R4, R5 and R6 are each independently selected from H or C. 1-4 alkyl.

[0020] In some embodiments of the present invention, when R1 is a substituted or unsubstituted aryl group, the aryl group is selected from phenanthrene, anthracene, indene, naphthalene, hydronaphthalene, benzyl, benzyloxy, and phenyl.

[0021] In some embodiments of the present invention, when R1 is a substituted aryl group, the substituent of the aryl group is selected from at least one of halogen, hydroxyl, aldehyde, acetal, ester, carbonyl, amide, cyano, substituted or unsubstituted aliphatic alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl.

[0022] In some preferred embodiments of the present invention, when R1 is a substituted aryl group, and the substituent of the aryl group is a substituted or unsubstituted heterocyclic alkyl group, the heterocyclic group is selected from substituted or unsubstituted thiophene and substituted or unsubstituted pyrrole.

[0023] In some embodiments of the present invention, when R1 is a substituted hydrocarbon group, the substituent of the hydrocarbon group is selected from C. 1-6 Alkoxycarbonyl, C 1-6 Alkoxycarbonylamino, C 1-6 alkyl group, C 1-6 Ester group, hydroxyl group, phenyl phosphoryl group, phenyl group, substituted phenyl group, benzyloxycarbonyl group, benzyloxycarbonylamino group, halogen, phenyl C 1-6 Acyl, substituted phenyl C 1-6 At least one of acyl, N-phthalimide, and substituted phenoxy groups.

[0024] In some embodiments of the present invention, when R1 is a substituted or unsubstituted hydrocarbon group, the substituted or unsubstituted hydrocarbon group is selected from substituted or unsubstituted C. 1-20 Aliphatic alkyl, substituted or unsubstituted C 3-20 One of the cycloalkyl groups.

[0025] In some preferred embodiments of the present invention, when R1 is a substituted or unsubstituted hydrocarbon group, the substituted or unsubstituted hydrocarbon group is selected from substituted or unsubstituted C. 1-10 Aliphatic alkyl, substituted or unsubstituted C 3-10 One of the cycloalkyl groups.

[0026] In some more preferred embodiments of the present invention, when R1 is a substituted or unsubstituted hydrocarbon group, the substituted or unsubstituted hydrocarbon group is selected from phenylphosphoryl, phenyl, substituted phenyl, benzyloxycarbonyl, benzyloxycarbonylamino, halogen, phenyl C 1-6 Acyl, substituted phenyl C 1-6 Acyl, N-phthalimide, substituted phenoxy, C 1-6 Alkoxycarbonyl, C 1-6 Alkoxycarbonylamino, C 1-6 alkyl group, C 1-6 One of ester group, hydroxyl group, or phenylphosphoyl group.

[0027] In some preferred embodiments of the present invention, the compound of formula (a) is selected from any one of the following:

[0028]

[0029] In some embodiments of the present invention, in formula (b), R2 and R3 are each independently selected from C 1-4When alkyl, the C 1-4 The alkyl group is selected from at least one of methyl, ethyl, isopropyl, and tert-butyl.

[0030] In some embodiments of the present invention, in formula (b), R4, R5, and R6 are each independently selected from C 1-4 When alkyl, the C 1-4 The alkyl group is methyl.

[0031] In some embodiments of the present invention, the anionic portion of the ionic nitrogen heterocyclic carbene ligand is a halide ion.

[0032] In some embodiments of the present invention, the ionic nitrogen heterocyclic carbene ligand is selected from any one of the following:

[0033]

[0034] In some preferred embodiments of the present invention, the ionic nitrogen heterocyclic carbene ligand is selected from any one of the following:

[0035]

[0036] In some embodiments of the present invention, the amount of the cobalt catalyst is 0.1%-10% of the molar amount of the compound of formula (a).

[0037] In some preferred embodiments of the present invention, the amount of the cobalt catalyst is 0.2%-5% of the molar amount of the compound of formula (a).

[0038] In some more preferred embodiments of the present invention, the amount of the cobalt catalyst is 0.5%-2% of the molar amount of the compound of formula (a).

[0039] In some embodiments of the present invention, the amount of the ionic nitrogen heterocyclic carbene ligand is 0.14%-14% of the molar amount of the compound of formula (a).

[0040] In some preferred embodiments of the present invention, the amount of the ionic nitrogen heterocyclic carbene ligand is 0.14%-7% of the molar amount of the compound of formula (a).

[0041] In some more preferred embodiments of the present invention, the amount of the ionic nitrogen heterocyclic carbene ligand is 0.28%-1.4% of the molar amount of the compound of formula (a).

[0042] In some embodiments of the present invention, the molar ratio of the boron reagent to the compound of formula (a) is (1-3):1.

[0043] In some preferred embodiments of the present invention, the molar ratio of the boron reagent to the compound of formula (a) is (1-2):1.

[0044] In some more preferred embodiments of the present invention, the molar ratio of the boron reagent to the compound of formula (a) is (1.2-1.5):1.

[0045] In some embodiments of the present invention, the molar ratio of the base to the ionic nitrogen heterocyclic carbene ligand is (3-5):1.

[0046] In some preferred embodiments of the present invention, the molar ratio of the base to the ionic nitrogen heterocyclic carbene ligand is (3.5-4.5):1.

[0047] In some embodiments of the present invention, the molar ratio of the cobalt catalyst to the ionic nitrogen heterocyclic carbene ligand is 1:(1-1.6).

[0048] In some embodiments of the present invention, the cobalt catalyst is selected from monovalent cobalt compounds or divalent cobalt compounds.

[0049] In some preferred embodiments of the present invention, the monovalent cobalt compound includes tris(triphenylphosphine)cobalt chloride (I).

[0050] In some preferred embodiments of the present invention, the divalent cobalt compound is selected from at least one of cobalt(II) acetylacetonate, cobalt(II) diiodocarbonylcyclopentadienyl, cobalt(II) di(hexafluoroacetylacetonate), cobalt(II) aluminate, cobalt(II) chlorate, cobalt(II) perchlorate, cobalt(II) fluoride, cobalt(II) hydroxide, cobalt(II) hydrated gluconate, cobalt(II) bis(trifluoromethanesulfonyl)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, cobalt(II) di(2,2,6,6-tetramethyl-3,5-heptadecanoate), and their hydrates.

[0051] In some embodiments of the present invention, the boron reagent is selected from at least one of pinacol diborate and neopentyl glycol diborate.

[0052] In some preferred embodiments of the present invention, the boron reagent is pinacol diborate (B2pin2).

[0053] In some embodiments of the present invention, the base is selected from at least one of nitrogen-containing organic bases having lone pairs of electrons and strong basic metal salts.

[0054] In some preferred embodiments of the present invention, the nitrogen-containing organic base having lone pair electrons is selected from at least one of alkylamines and nitrogen-substituted aromatic heterocycles.

[0055] In some more preferred embodiments of the present invention, the nitrogen-containing organic base having a lone pair electron is selected from triethylamine, tri-n-butylamine, diethylamine, morpholine, N-methylmorpholine, N-ethylmorpholine, cyclohexylamine, diisopropylamine, triethylenediamine, tetramethylguanidine, N,N-diisopropylethylamine, 1,8-diazabicyclo[5.4.0]undecyl-7-ene, 1,4-diazabicyclo[2.2.2]octane, pyridine, 4-dimethylaminopyridine, 2-dimethylaminopyridine, 2-methylpyridine, At least one of 2-methoxypyridine, 2-methylpyridine, 2-pyridinecarboxylic acid, 2,6-dimethylpyridine, 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, and quinine.

[0056] In some preferred embodiments of the present invention, the strongly alkaline metal salt is selected from at least one of 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, and potassium benzoate.

[0057] In some embodiments of the present invention, the reaction further includes the use of a solvent with a concentration of 0.1-0.3 mol / L; the ratio of the compound of formula (a) to the solvent is (0.1-1) mol: 1 mL.

[0058] In some preferred embodiments of the present invention, the solvent is selected from at least one of N,N-dimethylformamide (DMF), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMAc), and toluene (Tol).

[0059] In some embodiments of the present invention, the reaction temperature is 20-300°C and the time is 0.1-48h.

[0060] In some embodiments of the present invention, the inert atmosphere is selected from nitrogen or argon atmosphere.

[0061] In some embodiments of the present invention, after the reaction is completed, the product is further separated and purified to obtain the alkenyl geminoboronic ester; the separation and purification method is selected from at least one of extraction, column chromatography, distillation, decantation, filtration, centrifugation, washing, evaporation, stripping, and adsorption.

[0062] In some preferred embodiments of the present invention, the separation and purification are performed by extraction and column chromatography. Specifically, the solvent is washed away by extraction with ethyl acetate and water, the product is concentrated, and the concentrated residue is subjected to column chromatography.

[0063] In some embodiments of the present invention, the eluent for column chromatography is selected from at least one of n-hexane-ethyl acetate, dichloromethane-methanol, and petroleum ether-ethyl acetate.

[0064] In some embodiments of the present invention, the volume ratio of n-hexane to ethyl acetate is (5-100):1; the volume ratio of dichloromethane to methanol is (20-80):1; and the volume ratio of petroleum ether to ethyl acetate is (10-200):1.

[0065] In some embodiments of the present invention, the column chromatography includes the use of a 300-400 mesh silica gel column.

[0066] A second aspect of the present invention provides an alkenyl geminoboronate, comprising an alkenyl geminoboronate prepared by the preparation method described in the first aspect of the present invention, having the structural formula shown in formula (A). Wherein, R1 is selected from hydrogen, heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted hydrocarbon groups.

[0067] In some embodiments of the present invention, the alkenyl geminoboronic ester is shown as of Formulas 1-34:

[0068]

[0069]

[0070] The third aspect of the invention provides the use of the alkenyl geminolates described in the first aspect of the invention in the synthesis of polysubstituted olefins, natural products or pharmaceutical molecules.

[0071] Compared with the prior art, the beneficial effects of the present invention are:

[0072] 1) The method for preparing alkenyl geminosine esters provided by this invention uses a cobalt catalyst as the core. Under the combined action of a specific ionic nitrogen heterocyclic carbene ligand and a base, a highly active cobalt complex is formed. This complex can be reduced by boron to a catalytically active intermediate, thereby regenerating the cobalt catalyst and allowing it to continue catalyzing the next round of reactions. The cobalt catalyst used is abundant, inexpensive, 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, applicable not only to aromatic alkynes but also to aliphatic alkynes and sterically hindered alkynes; the reaction can be scaled up to gram-scale; and the product has high yield, selectivity, and purity.

[0073] 2) This invention uses inexpensive and readily available alkynes as reactants. Under an inert gas atmosphere, a diboration reaction is carried out to obtain the corresponding alkenyl geminiborates under the combined promotion of a cobalt catalyst, an ionic nitrogen heterocyclic carbene ligand, a base, and a boron reagent. The reaction has the advantages of low cost, mild conditions, high yield, and high selectivity, providing a new synthetic route and method for alkenyl geminiborates. It can provide structurally diverse alkenyl geminiborates for the synthesis of multisubstituted alkenes, natural products, or drug molecules. Detailed Implementation

[0074] The present invention will be further described in detail below through specific embodiments. Unless otherwise specified, the raw materials, reagents, or apparatus used in the embodiments can be obtained from conventional commercial sources or by existing technical methods. Unless otherwise specified, the experimental or testing methods are conventional methods in the art.

[0075] Example 1

[0076] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-phenyl-1-ethylene), and the steps and synthetic route are shown below:

[0077] Under a nitrogen atmosphere, phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.001 mmol, 0.005 equiv.), ligand L (0.0014 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0056 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a white solid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 96%.

[0078]

[0079] The product in Example 1 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0080] 1 H NMR (600MHz, CDCl3) δ7.72 (s, 1H), 7.48 (d, J = 7.3Hz, 2H), 7.32–7.26 (m, 3H), 1.31 (s, 12H), 1.28 (s, 12H).

[0081] 13 C NMR (151MHz, CDCl3) δ155.1,139.6,128.4,128.1,128.1,83.6,83.2,24.9,24.6.

[0082] 11 B NMR (193MHz, CDCl3) δ32.3,31.1.

[0083] Example 2

[0084] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[4-methyl-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0085] Under a nitrogen atmosphere, 4-methylphenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.002 mmol, 0.005 equiv.), ligand L (0.0028 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0112 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a colorless oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 93%.

[0086]

[0087] The product in Example 2 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0088] 1H NMR (400MHz, CDCl3) δ7.67(s,1H),7.38(d,J=8.1Hz,2H),7.10(d,J=8.0Hz,2H),2.32(s,3H),1.32(s,12H),1.27(s,12H).

[0089] 13 C NMR (151MHz, CDCl3) δ155.1,138.4,136.8,128.8,128.2,83.5,83.1,24.9,24.7,21.3.

[0090] 11 B NMR (193MHz, CDCl3) δ32.5,30.8.

[0091] Example 3

[0092] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[4-methoxy-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0093] Under a nitrogen atmosphere, 4-methoxyphenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.001 mmol, 0.005 equiv.), ligand L (0.0014 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0056 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a white solid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 94%.

[0094]

[0095] The product in Example 3 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0096] 1 H NMR (400MHz, CDCl3) δ7.65 (s, 1H), 7.44 (d, J = 8.7Hz, 2H), 6.82 (d, J = 8.8Hz, 2H), 3.80 (s, 3H), 1.32 (s, 12H), 1.27 (s, 12H).

[0097] 13 C NMR (151MHz, CDCl3) δ160.0,154.8,132.5,129.7,113.5,83.5,83.1,55.2,24.9,24.7.

[0098] 11 B NMR (193MHz, CDCl3) δ 31.0.

[0099] Example 4

[0100] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[4-dimethylamino-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0101] Under a nitrogen atmosphere, 4-dimethylaminophenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.004 mmol, 0.005 equiv.), ligand L (0.0056 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0224 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a yellow oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 87%.

[0102]

[0103] The product in Example 4 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0104] 1 H NMR (400MHz, CDCl3) δ7.62(s,1H),7.41(d,J=8.8Hz,2H),6.61(d,J=8.7Hz,2H),2.96(s,6H),1.34(s,12H),1.26(s,12H).

[0105] 13 C NMR (101MHz, CDCl3) δ155.7,150.8,129.9,128.1,111.7,83.5,83.0,40.5,25.0,24.9.

[0106] 11 B NMR (128MHz, CDCl3) δ 30.2.

[0107] Example 5

[0108] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[4-tert-butyl-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0109] Under a nitrogen atmosphere, 4-tert-butylphenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.001 mmol, 0.005 equiv.), ligand L (0.0014 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0056 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a white solid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 92%.

[0110]

[0111] The product in Example 5 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0112] 1 H NMR (400MHz, CDCl3) δ7.68 (s, 1H), 7.42 (d, J = 8.4Hz, 2H), 7.30 (d, J = 8.4Hz, 2H), 1.33 (s, 12H), 1.30 (s, 9H), 1.28 (s, 12H).

[0113] 13 C NMR (151MHz, CDCl3) δ155.1,151.7,136.8,128.1,125.1,83.6,83.2,34.7,31.4,25.0,24.8.

[0114] 11 B NMR (193MHz, CDCl3) δ 30.8.

[0115] Example 6

[0116] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[4-acetamido-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0117] Under a nitrogen atmosphere, 4-acetamido-phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.004 mmol, 0.005 equiv.), ligand L (0.0056 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0224 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a colorless oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 60%.

[0118]

[0119] The product in Example 6 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0120] 1 H NMR (400MHz, CDCl3) δ7.64(s,1H),7.47-7.42(m,5H),2.15(s,3H),1.32(s,12H),1.27(s,12H).

[0121] 13 C NMR (151MHz, CDCl3) δ168.3,154.5,138.3,135.4,128.9,119.1,83.7,83.2,24.9,24.7.

[0122] 11 B NMR (193MHz, CDCl3) δ31.2.

[0123] Example 7

[0124] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[4-trifluoromethoxy-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0125] Under a nitrogen atmosphere, 4-trifluoromethoxy-phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.002 mmol, 0.005 equiv.), ligand L (0.0028 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0112 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a white solid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 72%.

[0126]

[0127] The product in Example 7 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR, 11 B NMR and 19 F NMR characterization, the results are as follows:

[0128] 1 H NMR (600MHz, CDCl3) δ7.67 (s, 1H), 7.50 (d, J = 8.6Hz, 2H), 7.13 (d, J = 8.2Hz, 2H), 1.30 (s, 12H), 1.28 (s, 12H).

[0129] 13 C NMR (151MHz, CDCl3) δ153.3,149.2,138.4,129.6,120.5,83.8,83.4,24.9,24.7.

[0130] 11 B NMR (193MHz, CDCl3) δ 30.5.

[0131] 19 F NMR (565MHz, CDCl3) δ -57.8.

[0132] Example 8

[0133] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[4-fluoro-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0134] Under a nitrogen atmosphere, 4-fluoro-phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.004 mmol, 0.005 equiv.), ligand L (0.0056 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0224 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a white solid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 86%.

[0135]

[0136] The product in Example 8 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR, 11 B NMR and 19 F NMR characterization, the results are as follows:

[0137] 1 H NMR (600MHz, CDCl3) δ7.65 (s, 1H), 7.48–7.43 (m, 2H), 6.97 (app.t, J = 8.4Hz, 2H), 1.30 (s, 12H), 1.26 (s, 12H).

[0138] 13 C NMR (151MHz, CDCl3) δ162.8 (d, J = 248.2Hz), 153.8, 135.8 (d, J = 3.0Hz), 129.9 (d, J = 8.2Hz), 115.0 (d, J = 21.5Hz), 83.6, 83.2, 24.8, 24.6.

[0139] 11 B NMR (193MHz, CDCl3) δ 30.9.

[0140] 19 F NMR (565MHz, CDCl3) δ-113.1.

[0141] Example 9

[0142] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[4-chloro-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0143] Under a nitrogen atmosphere, 4-chloro-phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.004 mmol, 0.005 equiv.), ligand L (0.0056 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0224 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a white solid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 75%.

[0144]

[0145] The product in Example 9 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0146] 1 H NMR (400MHz, CDCl3) δ7.57 (s, 1H), 7.35 (d, J = 8.4Hz, 2H), 7.19 (d, J = 8.4Hz, 2H), 1.24 (s, 12H), 1.20 (s, 12H).

[0147] 13 C NMR (151MHz, CDCl3) δ153.5,138.1,134.2,129.4,128.3,83.7,83.3,24.9,24.7.

[0148] 11 B NMR (193MHz, CDCl3) δ 30.6.

[0149] Example 10

[0150] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[3-methyl-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0151] Under a nitrogen atmosphere, 3-methyl-phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.001 mmol, 0.005 equiv.), ligand L (0.0014 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0056 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a colorless oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 96%.

[0152] The product in Example 10 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0153] 1 H NMR (400MHz, CDCl3) δ7.69 (s, 1H), 7.33 (s, 1H), 7.26 (d, J = 7.6Hz, 1H), 7.19 (app. t,J=7.6Hz,1H),7.07(d,J=7.5Hz,1H),2.32(s,3H),1.32(s,12H),1.27(s,12H).

[0154] 13 C NMR (151MHz, CDCl3) δ155.4,139.6,137.6,129.2,128.5,128.0,125.6,83.5,83.2,24.9,24.7,21.3.

[0155] 11 B NMR (193MHz, CDCl3) δ32.5,31.0.

[0156] Example 11

[0157] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[3-methoxy-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0158] Under a nitrogen atmosphere, 3-methoxy-phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.001 mmol, 0.005 equiv.), ligand L (0.0014 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0056 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a colorless oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 94%.

[0159]

[0160] The product in Example 11 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0161] 1 H NMR (400MHz, CDCl3) δ7.68 (s, 1H), 7.20 (app.t, J = 7.9Hz, 1H), 7.09 (d, J = 7.7Hz, 1H) ,7.01(s,1H),6.81(dd,J=7.9,2.2Hz,1H),3.78(s,3H),1.30(s,12H),1.27(s,12H).

[0162] 13 C NMR (151MHz, CDCl3) δ159.5,155.0,141.2,129.0,120.5,114.1,113.8,83.6,83.2,55.3,24.9,24.7.

[0163] 11 B NMR (193MHz, CDCl3) δ32.4,31.2.

[0164] Example 12

[0165] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[3-chloro-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0166] Under a nitrogen atmosphere, 3-chloro-phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.004 mmol, 0.005 equiv.), ligand L (0.0056 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0224 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask, along with 1 mL of anhydrous DMF. The mixture was stirred at 120 °C for 12 h. After the reaction was complete, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. The product was separated by column chromatography to obtain a white solid product (eluent: petroleum ether-ethyl acetate) in 55% yield.

[0167]

[0168] The product in Example 12 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0169] 1 H NMR (600MHz, CDCl3) δ7.63(s,1H),7.55(s,1H),7.30–7.28(m,1H),7.23–7.22(m,2H),1.32(s,12H),1.28(s,12H).

[0170] 13 C NMR (151MHz, CDCl3) δ153.3,141.4,134.2,129.4,128.3,127.5,126.8,83.8,83.4,24.9,24.7.

[0171] 11 B NMR (193MHz, CDCl3) δ 31.4.

[0172] The high-resolution mass spectrometry characterization results are: HRMS(ESI+) m / z calculated for C 20 H 29 B2ClO4Na + ([M+H)) + 413.1833; found 413.1845.

[0173] Example 13

[0174] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[2-methyl-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0175] Under a nitrogen atmosphere, 2-methyl-phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.002 mmol, 0.005 equiv.), ligand L (0.0028 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0112 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a colorless oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 85%.

[0176]

[0177] The product in Example 13 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0178] 1 H NMR (400MHz, CDCl3) δ7.89 (s, 1H), 7.45 (d, J = 7.0Hz, 1H), 7.17–7.13 (m, 1H), 7.12–7.07 (m, 2H), 2.35 (s, 3H), 1.27 (s, 12H), 1.23 (s, 12H).

[0179] 13 C NMR (151MHz, CDCl3) δ154.2,139.2,136.3,129.8,128.3,127.7,125.5,83.5,83.1,24.9,24.6,19.8.

[0180] 11 B NMR (193MHz, CDCl3) δ 30.7.

[0181] Example 14

[0182] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[2-methoxy-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0183] Under a nitrogen atmosphere, 2-methoxy-phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.002 mmol, 0.005 equiv.), ligand L (0.0028 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0112 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a colorless oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 93%.

[0184]

[0185] The product in Example 14 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0186] 1 H NMR (400MHz, CDCl3) δ7.96 (s, 1H), 7.47 (dd, J=7.6, 1.5Hz, 1H), 7.21 (app.td, J=8.2, 1. 6Hz, 1H), 6.82 (app.t, J=7.5Hz, 1H), 6.79 (d, J=8.2Hz, 1H), 3.77 (s, 3H), 1.24 (m, 24H).

[0187] 13 C NMR (151MHz, CDCl3) δ157.3,151.0,129.8,129.1,128.7,119.9,110.4,83.4,83.0,55.3,24.9,24.6.

[0188] 11 B NMR (193MHz, CDCl3) δ31.9,31.1.

[0189] Example 15

[0190] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[2-chloro-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0191] Under a nitrogen atmosphere, 2-chloro-phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.001 mmol, 0.005 equiv.), ligand L (0.0014 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0056 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a white solid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 61%.

[0192]

[0193] The product in Example 15 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0194] 1 H NMR (400MHz, CDCl3) δ7.92(s,1H),7.56(dd,J=7.1,2.1Hz,1H),7.32(dd,J=7.4,1.8Hz,1H),7.22–7.15(m,2H),1.28(s,12H),1.25(s,12H).

[0195] 13 C NMR (151MHz, CDCl3) δ151.7,138.1,133.8,129.4,129.4,129.2,126.2,83.7,83.3,24.9,24.6.

[0196] 11 B NMR (193MHz, CDCl3) δ32.3,30.4.

[0197] Example 16

[0198] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[2-isopropyl-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0199] Under a nitrogen atmosphere, 2-isopropyl-phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.001 mmol, 0.005 equiv.), ligand L (0.0014 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0056 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a colorless oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 93%.

[0200]

[0201] The product in Example 16 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0202] 1 H NMR (600MHz, CDCl3) δ8.00 (s, 1H), 7.38 (d, J = 7.7Hz, 1H), 7.23 (s, 2H), 7.09-7.07 (m ,1H),3.23(hept,J=6.9Hz,1H),1.28(s,12H),1.22(d,J=6.8Hz,6H),1.18(s,12H).

[0203] 13 C NMR (151MHz, CDCl3) δ154.7,146.6,138.6,128.4,128.4,125.2,124.5,83.4,83.1,29.4,24.9,24.5,23.5.

[0204] 11 B NMR (193MHz, CDCl3) δ 33.2.

[0205] The high-resolution mass spectrometry characterization results are: HRMS(ESI+) m / z calculated for C 23 H 36 B2O8Na + ([M+Na)) + )421.2692; found421.2693.

[0206] Example 17

[0207] This embodiment prepares an alkenyl geminoboronic ester (1,1'-bispinacolboronic acid ester-2-[2-methoxy,6-fluoro-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0208] Under a nitrogen atmosphere, 2-methoxy,6-fluoro-phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.004 mmol, 0.005 equiv.), ligand L (0.0056 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0224 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a colorless oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 97%.

[0209]

[0210] The product in Example 17 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR, 11 B NMR and 19 F NMR characterization, the results are as follows:

[0211] 1 H NMR (400MHz, CDCl3) δ7.64(s,1H),7.17–7.11(m,1H),6.64-6.60(m,2H),3.79(s,3H),1.27(s,12H),1.21(s,12H).

[0212] 13 C NMR (101MHz, CDCl3) δ160.6 (d, J = 247.6Hz), 158.5 (d, J = 7.4Hz), 144.5, 129.1 (d, J = 11.0Hz), 117.2(d,J=15.6Hz),107.9(d,J=23.3Hz),106.4(d,J=2.7Hz),83.1,83.0,56.0,24.9,24.7.

[0213] 11 B NMR (128MHz, CDCl3) δ 29.6.

[0214] 19 F NMR (377MHz, CDCl3) δ-112.5.

[0215] The high-resolution mass spectrometry characterization results are: HRMS(ESI+) m / z calculated for C 21 H 31 B2FO5Na + ([M+Na)) + 427.2234; found 427.2223.

[0216] Example 18

[0217] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[2,6-dimethoxy-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0218] Under a nitrogen atmosphere, 2,6-dimethoxy-phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.002 mmol, 0.005 equiv.), ligand L (0.0028 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0112 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a white solid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 88%.

[0219]

[0220] The product in Example 18 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0221] 1 H NMR (400MHz, CDCl3) δ7.71 (s, 1H), 7.14 (t, J = 8.3Hz, 1H), 6.50 (d, J = 8.3Hz, 2H), 3.76 (s, 6H), 1.27 (s, 12H), 1.20 (s, 12H).

[0222] 13 C NMR (101MHz, CDCl3) δ158.1,146.7,128.9,118.1,104.3,82.8,82.6,55.8,25.0,24.8.

[0223] 11B NMR (128MHz, CDCl3) δ 30.4.

[0224] The high-resolution mass spectrometry characterization results are: HRMS(ESI+) m / z calculated for C 22 H 34 B2O6Na + ([M+Na)) + )439.2434; found439.2436.

[0225] Example 19

[0226] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[3,5-dimethoxy-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0227] Under a nitrogen atmosphere, 3,5-dimethoxy-phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.001 mmol, 0.005 equiv.), ligand L (0.0014 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0056 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a white solid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 87%.

[0228]

[0229] The product in Example 19 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0230] 1 H NMR (600MHz, CDCl3) δ7.64(s,1H),6.64(s,2H),6.37(s,1H),3.76(s,6H),1.29(s,12H),1.26(s,12H).

[0231] 13 C NMR (151MHz, CDCl3) δ160.6,155.0,141.9,106.3,100.6,83.6,83.2,55.3,24.9,24.7.

[0232] 11 B NMR (193MHz, CDCl3) δ 30.8.

[0233] The high-resolution mass spectrometry characterization results are: HRMS(ESI+) m / z calculated for C 22 H 35 B2O6 + ([M+H)) + 417.2614; found 417.2616.

[0234] Example 20

[0235] This embodiment prepares an alkenyl geminoboronic ester (1,1'-bispinacolboronic acid ester-2-[2,4,6-trimethyl-phenyl]-1-ethylene), and the steps and synthetic route are shown below:

[0236] Under a nitrogen atmosphere, 2,4,6-trimethyl-phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.002 mmol, 0.005 equiv.), ligand L (0.0028 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0112 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a white solid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 91%.

[0237]

[0238] The product in Example 20 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0239] 1 H NMR (400MHz, CDCl3) δ7.67(s,1H),6.77(s,2H),2.23(s,3H),2.19(s,6H),1.29(s,12H),0.98(s,12H).

[0240] 13C NMR (101MHz, CDCl3) δ156.6,137.7,135.9,135.1,127.3,83.1,83.0,25.0,24.2,20.9,20.4.

[0241] 11 B NMR (128MHz, CDCl3) δ 30.8.

[0242] The high-resolution mass spectrometry characterization results are: HRMS(ESI+) m / z calculated for C 23 H 36 B2O4Na + ([M+Na)) + )421.2692; found421.2696.

[0243] Example 21

[0244] This embodiment prepares an alkenyl geminoboronic ester (1,1'-bispinarylboronic acid ester-2-[thiophen-3-yl]-ethylene), and the steps and synthetic route are shown below:

[0245] Under a nitrogen atmosphere, 3-ethynylthiophene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.004 mmol, 0.005 equiv.), ligand L (0.0056 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0224 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a white solid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 78%.

[0246]

[0247] The product in Example 21 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0248] 1H NMR (600MHz, CDCl3) δ7.64(s,1H),7.44(d,J=2.8Hz,1H),7.31(d,J=5.0Hz,1H),7.21(dd,J=5.0,3.0Hz,1H),1.33(s,12H),1.27(s,12H).

[0249] 13 C NMR (151MHz, CDCl3) δ148.2,142.5,127.2,125.6,125.3,83.6,83.1,24.8,24.8.

[0250] 11 B NMR (193MHz, CDCl3) δ31.1.

[0251] Example 22

[0252] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-[1-naphthyl]-ethylene), and the steps and synthetic route are shown below:

[0253] Under a nitrogen atmosphere, 1-ethynylnaphthalene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.001 mmol, 0.005 equiv.), ligand L (0.0014 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0056 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a white solid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 89%.

[0254]

[0255] The product in Example 22 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0256] 1H NMR (400MHz, CDCl3) δ8.43(s,1H),8.14(d,J=7.2Hz,1H),7.83(dd,J=6.8,2.6Hz,1H),7.78(d,J=8.2Hz ,1H),7.63(d,J=7.1Hz,1H),7.52–7.45(m,2H),7.40(app.t,J=7.7Hz,1H),1.33(s,12H),1.18(s,12H).

[0257] 13 C NMR (101MHz, CDCl3) δ153.6,137.8,133.3,131.4,128.7,128.2,126.0,125.8,125.5,125.1,124.9,83.5,83.3,25.0,24.5.

[0258] 11 B NMR (128MHz, CDCl3) δ 30.9.

[0259] Example 23

[0260] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinnazolinone-1-[2-naphthyl]-ethylene), and the steps and synthetic route are shown below:

[0261] Under a nitrogen atmosphere, 2-ethynylnaphthalene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.002 mmol, 0.005 equiv.), ligand L (0.0028 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0112 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a white solid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 79%.

[0262] The product in Example 23 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0263] 1H NMR(400MHz, CDCl3)δ7.96(s,1H),7.89(s,1H),7.81–7.76(m,3H),7.64(dd, J=8.5,1.6Hz,1H),7.45(dd,J=6.2,3.2Hz,2H),1.34(s,12H),1.31(s,12H).

[0264] 13 C NMR (101MHz, CDCl3) δ155.1,137.3,133.4,133.3,128.3,127.8,127.7,127.7,126.2,126.1,125.9,83.7,83.3,24.9,24.8.

[0265] 11 B NMR (128MHz, CDCl3) δ 31.2.

[0266] Example 24

[0267] This embodiment prepares an alkenyl geminoboronic ester (1,1'-bipinnazolate-2-[9-phenanthyl]-ethylene), and the steps and synthetic route are shown below:

[0268] Under a nitrogen atmosphere, 9-ethynylphenanthrene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.002 mmol, 0.005 equiv.), ligand L (0.0028 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0112 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a white solid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 91%.

[0269]

[0270] The product in Example 24 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0271] 1H NMR (600MHz, CDCl3) δ8.70(d,J=8.0Hz,1H),8.65(d,J=8.2Hz,1H),8.42(s,1H),8.18(d,J=7.9Hz,1H), 7.91(s,1H),7.84(d,J=7.3Hz,1H),7.67–7.60(m,3H),7.58-7.56(m,1H),1.35(s,12H),1.16(s,12H).

[0272] 13 C NMR (151MHz, CDCl3) δ153.9,136.9,131.5,130.6,130.6,130.1,128.7,126. 7,126.6,126.6,126.5,126.3,125.8,122.8,122.6,83.5,83.3,25.0,24.6.

[0273] 11 B NMR (193MHz, CDCl3) δ 32.2.

[0274] The high-resolution mass spectrometry characterization results are: HRMS(ESI+) m / z calculated for C 28 H 34 B2O4Na + ([M+Na)) + 479.2535; found 479.2548.

[0275] Example 25

[0276] This embodiment prepares an alkenyl geminoboronic ester (1,4-bis-[2,2'-bispinarylboronic ester-vinyl]-benzene), and the steps and synthetic route are shown below:

[0277] Under a nitrogen atmosphere, 1,4-diethynylbenzene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.004 mmol, 0.005 equiv.), ligand L (0.0056 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0224 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a white solid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 47%.

[0278]

[0279] The product in Example 25 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0280] 1 H NMR (400MHz, CDCl3) δ7.66(s,2H),7.42(s,4H),1.30(s,24H),1.26(s,24H).

[0281] 13 C NMR (151MHz, CDCl3) δ154.7,139.8,128.2,83.8,83.4,25.0,24.8.

[0282] 11 B NMR (193MHz, CDCl3) δ31.3.

[0283] The high-resolution mass spectrometry characterization results are: HRMS(ESI+) m / z calculated for C 34 H 54 B4O8Na + ([M+Na)) + )657.4083; found657.4090.

[0284] Example 26

[0285] This embodiment prepares an alkenyl geminoboronate (1,1'-bispinalanoboronate-1-octene), and the steps and synthetic route are shown below:

[0286] Under a nitrogen atmosphere, 1-octyne (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.004 mmol, 0.005 equiv.), ligand L (0.0056 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0224 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous THF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a colorless oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 83%.

[0287]

[0288] The product in Example 26 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0289] 1 H NMR(400MHz, CDCl3) δ6.95(t,J=7.2Hz,1H),2.27(q,J=7.3Hz,2H),1.43(dt, J=14.8,7.3Hz,2H),1.31-1.29(m,18H),1.25(s,12H),0.89(t,J=6.8Hz,3H).

[0290] 13 C NMR (101MHz, CDCl3) δ162.6,83.1,82.8,35.5,31.7,29.0,29.0,24.8,24.7,22.6,14.1.

[0291] 11 B NMR (128MHz, CDCl3) δ 31.4.

[0292] Example 27

[0293] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinarylboronic acid ester-3-cyclohexyl-1-propene), and the steps and synthetic route are shown below:

[0294] Under a nitrogen atmosphere, 3-cyclohexyl-1-propyne (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.004 mmol, 0.005 equiv.), ligand L (0.0056 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.00224 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous THF (1 mL) was added, and the mixture was stirred at 120 °C for 12 h. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a colorless oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 64%.

[0295] The product in Example 27 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0296] 1H NMR(600MHz, CDCl3)δ6.93(t,J=7.3Hz,1H),2.15(app.t,J=7.1Hz,2H),1.71–1.65(m,4H ),1.43–1.35(m,1H),1.29(s,12H),1.22(s,12H),1.19–1.09(m,4H),0.93–0.87(m,2H).

[0297] 13 C NMR (151MHz, CDCl3) δ161.1,83.1,82.8,43.2,37.8,33.3,26.5,26.3,24.8,24.7.

[0298] 11 B NMR (193MHz, CDCl3) δ 31.7.

[0299] The high-resolution mass spectrometry characterization results are: HRMS(ESI+) m / z calculated for C 21 H 38 B2O4Na + ([M+Na)) + )399.2848; found399.2859.

[0300] Example 28

[0301] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-4-phenyl-1-butene), and the steps and synthetic route are shown below:

[0302] Under a nitrogen atmosphere, 4-phenyl-1-butyne (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.01 mmol, 0.005 equiv.), ligand L (0.014 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.056 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous THF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a colorless oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 76%.

[0303] The product in Example 28 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0304] 1 H NMR (400MHz, CDCl3) δ7.32–7.28(m,2H),7.22–7.18(m,3H),7.05(t,J=7.1 Hz,1H),2.77-2.74(m,2H),2.64-2.58(m,2H),1.31(s,12H),1.27(s,12H).

[0305] 13 C NMR (151MHz, CDCl3) δ161.4,142.1,128.3,125.7,83.2,82.9,37.3,35.6,24.8,24.8.

[0306] 11 B NMR (193MHz, CDCl3) δ 32.0.

[0307] Example 29

[0308] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-3-[tert-butyldimethylsiloxy]-1-propene), and the steps and synthetic route are shown below:

[0309] Under a nitrogen atmosphere, 3-tert-butyldimethylsiloxy-1-propyne (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.01 mmol, 0.005 equiv.), ligand L (0.014 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.056 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous THF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a colorless oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 72%.

[0310]

[0311] The product in Example 29 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0312] 1H NMR (600MHz, CDCl3) δ6.97 (t, J = 4.8 Hz, 1H), 4.37 (d, J = 5.4 Hz, 2H), 1.26 (s, 12H), 1.22 (s, 12H), 0.88 (s, 9H), 0.04 (s, 6H).

[0313] 13 C NMR (151MHz, CDCl3) δ162.0,83.2,83.0,65.3,26.0,25.0,24.8,18.4,-5.1.

[0314] 11 B NMR (193MHz, CDCl3) δ31.2.

[0315] Example 30

[0316] This embodiment prepares an alkenyl geminoboronate (1,1'-bispinarylboronate-5-acrylonitrile-1-pentene), and the steps and synthetic route are shown below:

[0317] Under a nitrogen atmosphere, 5-acrylonitrile-1-pentyne (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.004 mmol, 0.005 equiv.), ligand L (0.0056 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0224 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous THF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a colorless oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 78%.

[0318]

[0319] The product in Example 30 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0320] 1 H NMR (600MHz, CDCl3) δ6.79(s,1H),2.40-2.39(m,2H),2.32-2.31(m,2H),1.79–1.78(m,2H),1.27(s,12H),1.22(s,12H).

[0321] 13C NMR (151MHz, CDCl3) δ158.6,119.7,83.4,83.1,33.8,24.8,24.8,24.7,16.5.

[0322] 11 B NMR (193MHz, CDCl3) δ 31.7.

[0323] Example 31

[0324] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-5-phthalimide-1-pentene), and the steps and synthetic route are shown below:

[0325] Under a nitrogen atmosphere, 5-phthalimide-1-pentyne (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.004 mmol, 0.005 equiv.), ligand L (0.0056 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0224 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous THF (1 mL) was added, and the mixture was stirred at 120 °C for 12 h. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a colorless oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 81%.

[0326]

[0327] The product in Example 31 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0328] 1 H NMR (600MHz, CDCl3) δ7.85 (dd, J=5.4, 3.0Hz, 2H), 7.72 (dd, J=5.4, 3.0Hz, 2H), 6.94 (t, J=7.1Hz, 1H), 3. 71(t,J=7.3Hz,2H),2.36(app.q,J=7.3Hz,2H),1.84(app.p,J=7.6Hz,2H),1.27(s,12H),1.24(s,12H).

[0329] 13C NMR (151MHz, CDCl3) δ168.2,160.4,133.8,132.2,123.1,83.1,82.9,37.9,32.7,28.0,24.8,24.7.

[0330] 11 B NMR (193MHz, CDCl3) δ31.3.

[0331] Example 32

[0332] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-3-methyl-1-butene), and the steps and synthetic route are shown below:

[0333] Under a nitrogen atmosphere, 3-methyl-1-butyne (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.01 mmol, 0.005 equiv.), ligand L (0.014 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.056 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous THF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a colorless oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 50%.

[0334]

[0335] The product in Example 32 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0336] 1 H NMR (600MHz, CDCl3) δ6.71 (d, J = 9.0Hz, 1H), 2.60 (dhept, J = 9.1, 6.7Hz, 1H), 1.28 (s, 12H), 1.22 (s, 12H), 0.99 (d, J = 6.6Hz, 6H).

[0337] 13 C NMR (151MHz, CDCl3) δ176.6,168.4,83.1,82.8,34.3,24.8,24.7,22.6.

[0338] 11B NMR (193MHz, CDCl3) δ31.6,30.8.

[0339] The high-resolution mass spectrometry characterization results are: HRMS(ESI+) m / z calculated for C 17 H 32 B2O4Na + ([M+Na)) + )345.2379; found345.2380.

[0340] Example 33

[0341] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinacolboronic acid ester-2-cyclopentylethylene), and the steps and synthetic route are shown below:

[0342] Under a nitrogen atmosphere, cyclopentylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.01 mmol, 0.005 equiv.), ligand L (0.014 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.056 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous THF (1 mL) was added, and the mixture was stirred at 120 °C for 60 min. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a colorless oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 79%.

[0343]

[0344] The product in Example 33 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0345] 1 H NMR(600MHz, CDCl3)δ6.80(d,J=9.0Hz,1H),2.74–2.67(m,1H),1.82–1.77(m,2H),1 .65-1.61(m,2H),1.55–1.50(m,2H),1.34–1.31(m,2H),1.27(s,12H),1.21(s,12H).

[0346] 13C NMR (151MHz, CDCl3) δ166.9,83.1,82.8,45.9,33.4,25.8,24.8,24.7.

[0347] 11 B NMR (193MHz, CDCl3) δ 31.5.

[0348] The high-resolution mass spectrometry characterization results are: HRMS(ESI+) m / z calculated for C 19 H 34 B2O4Na + ([M+Na)) + )371.2535; found371.2536.

[0349] Example 34

[0350] This embodiment prepares an alkenyl geminoboronic acid ester (1,1'-bispinarylboronic acid ester-2-cyclohexylethylene), and the steps and synthetic route are shown below:

[0351] Under a nitrogen atmosphere, cyclohexylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.004 mmol, 0.005 equiv.), ligand L (0.0056 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.3 mmol, 1.5 equiv.), and potassium tert-butoxide (0.0224 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous THF (1 mL) was added, and the mixture was stirred at 120 °C for 12 h. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. After separation by column chromatography, a colorless oily liquid product (eluent: petroleum ether-ethyl acetate) was obtained with a yield of 52%.

[0352]

[0353] The product in Example 34 was analyzed using nuclear magnetic resonance. 1 H NMR, 13 C NMR and 11 B NMR characterization, the results are as follows:

[0354] 1 H NMR (400MHz, Chloroform-d) δ6.74(d,J=8.8Hz,1H),2.31-2.21(m,1H),1.72–1.67(m,4H),1.29(s,12H),1.22(s,12H),1.19–1.06(m,6H).

[0355] 13 C NMR (151MHz, CDCl3) δ167.1,83.1,82.8,44.2,32.7,25.9,25.8,24.8,24.7.

[0356] 11 B NMR (193MHz, CDCl3) δ 31.7.

[0357] Example 35

[0358] This example investigates the effect of different ionic nitrogen heterocyclic carbene ligands on the yield of alkenyl geminosine diboronic acid esters. The steps are as follows:

[0359] Under a nitrogen atmosphere, phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.004 mmol, 0.005 equiv.), ionic nitrogen-containing heterocyclic carbene ligand (0.0056 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.4 mmol, 2 equiv.), and potassium tert-butoxide (0.0224 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the mixture was stirred at 120 °C for 12 h. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. The product was obtained by column chromatography (eluent: petroleum ether-ethyl acetate), and the yield was calculated. The structure of the ionic nitrogen-containing heterocyclic carbene ligand is shown in Table 1.

[0360] Table 1 Effect of ionic nitrogen heterocyclic carbene ligands on product yield

[0361]

[0362] Table 1 shows the effect of ionic nitrogen heterocyclic carbene ligands on product yield. As can be seen from Table 1, when the reaction substrate and reaction conditions are the same, the structure of ionic nitrogen heterocyclic carbene ligands has a significant impact on product yield.

[0363] Example 36

[0364] This example investigates the effect of different solvents on the yield of alkenyl geminoboronates. The steps are as follows:

[0365] Under a nitrogen atmosphere, phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.001 mmol, 0.005 equiv.), ligand CNC-Me (0.0014 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.4 mmol, 2 equiv.), and potassium tert-butoxide (0.0056 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Solvent (1 mL) was added, and the mixture was stirred at 120 °C. After the reaction was complete, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. The product was obtained by column chromatography (eluent: petroleum ether-ethyl acetate), and the yield was calculated. The types of solvents are shown in Table 2.

[0366] Table 2 Effect of solvent on product yield

[0367] solvent Reaction time (h) Yield (%) DMF 12 ＞99 THF 12 97 <![CDATA[CH3CN]]> 12 ＜1 DMF 1 ＞99 THF 1 78

[0368] Table 2 shows the effect of solvent on product yield. As can be seen from Table 2, different solvents will affect the product yield. Using amide solvents such as DMF, the reaction efficiency is the best, and the product yield can reach more than 99% after 1 hour of reaction. Ether solvents such as THF can also be used as suitable reaction solvents.

[0369] Example 37

[0370] This example investigates the effect of different cobalt catalysts on the yield of alkenyl geminoboronates. The steps are as follows:

[0371] Under a nitrogen atmosphere, phenylacetylene (0.2 mmol, 1 equiv.), cobalt catalyst (0.001 mmol, 0.005 equiv.), ligand CNC-Me (0.0014 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate (0.4 mmol, 2 equiv.), and potassium tert-butoxide (0.0056 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the reaction was stirred at 120 °C. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. The product was obtained by column chromatography (eluent: petroleum ether-ethyl acetate), and the yield was calculated. The types of cobalt catalysts are shown in Table 3.

[0372] Table 3 Effect of cobalt catalyst on product yield

[0373]

[0374]

[0375] Table 3 shows the effect of cobalt catalysts on product yield. As can be seen from Table 3, cobalt(II) acetylacetonate has the highest catalytic activity, and the yield can reach more than 99% after 0.5 h of reaction. Other divalent cobalt catalysts also have very good catalytic activity. For monovalent cobalt Co(PPh3)3Cl catalyst, the reaction time needs to be extended to improve the yield.

[0376] Example 38

[0377] This embodiment investigates the effect of the amount of boron reagent on the yield of alkenyl geminoboronate, and the steps are as follows:

[0378] Under a nitrogen atmosphere, phenylacetylene (0.2 mmol, 1 equiv.), cobalt(II) acetylacetonate (0.001 mmol, 0.005 equiv.), ligand CNC-Me (0.0014 mmol, 1.4 equivalents to cobalt catalyst), pinacol diboronate, and potassium tert-butoxide (0.0056 mmol, 4 equivalents to ligand) were added to a 5 mL reaction flask. Anhydrous DMF (1 mL) was added, and the reaction was stirred at 120 °C. After the reaction was completed, water and ethyl acetate were added for extraction. The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated. The product was obtained by column chromatography (eluent: petroleum ether-ethyl acetate), and the yield was calculated. The amount of pinacol diboronate used is shown in Table 4.

[0379] Table 4 Effect of boron reagent dosage on product yield

[0380] The dosage of piperyl borate relative to phenylacetylene Yield (%) 3 equivalent ＞99 2 equivalent ＞99 1.5 equivalent ＞99 1.1 equivalent 83

[0381] Table 4 shows the effect of the amount of boron reagent on the product yield. As can be seen from Table 4, the amount of boron reagent, piperyl borate, can be flexibly varied. When the amount of boron reagent is 1-3 equivalents relative to the substrate, a high yield can be obtained.

[0382] Example 39

[0383] This embodiment explores the practical application value of the preparation method of alkenyl geminosine diboronic acid esters. The steps are as follows:

[0384] Under a nitrogen atmosphere, phenylacetylene (20 mmol), cobalt(II) acetylacetonate (0.2 mmol), ligand CNC-Me (0.28 mmol), pinacol diboronate (22 mmol), and potassium tert-butoxide (1.1 mmol) were added to a 30 mL reaction flask, followed by anhydrous DMF (30 mL). The mixture was stirred at 120 °C for 60 min. After the reaction was completed, 4-cyanopyridine was added and heated to remove excess pinacol diboronate. The mixture was then directly extracted and washed to obtain 7.3 g of pure product, with a product yield of 99%.

[0385] The only difference between this embodiment and Example 1 is the scale of the reaction. It was found that at a scale of 20 mmol phenylacetylene, the amount of solvent and the amount of bipinnatol borate ester can be further reduced, and the product with a yield of up to 99% can still be obtained. The product does not require column chromatography purification, indicating that the preparation method of alkenyl geminitroborates provided by this invention can meet the needs of industrialization and has good practical application value.

[0386] Example 40

[0387] This embodiment investigates the effect of different bases on product yield, and the steps are as follows:

[0388] The reaction was carried out under different base conditions with 0.0014 mmol CNC-Me as ligand, 0.001 mmol of cobalt(II) acetylacetonate, 1 mL of anhydrous DMF as solvent, 0.0056 mmol of potassium tert-butoxide, 0.2 mmol of phenylacetylene, and 1.5 equivalents of phenylacetylene in the amount of bipinnatyl borate. The reaction steps were the same as in Example 1.

[0389] Table 5 Effect of alkali on product yield

[0390] alkali Yield (%) alkali Yield (%) Potassium tert-butoxide 99 Sodium ethoxide 89 Potassium carbonate 89 Sodium methoxide 87 cesium carbonate 79 Sodium hydroxide 70 Sodium tert-butoxide 81 potassium hydroxide 75

[0391] Table 5 shows the effect of alkali on product yield. As can be seen from Table 5, high yields can be obtained by using various strong basic metal salts as alkalis in the reaction, among which potassium tert-butoxide has the best effect.

[0392] Example 41

[0393] This embodiment investigates the effect of reaction conditions on product yield, and the steps are as follows:

[0394] Using 0.0014 mmol CNC-Me as the ligand, 0.001 mmol of cobalt(II) acetylacetonate, 1 mL of anhydrous DMF as the solvent, 0.0056 mmol of potassium tert-butoxide, 0.2 mmol of phenylacetylene, and 1.5 equivalents of phenylacetylene in the amount of bipinnatyl borate, the catalyst, ligand, and base were omitted accordingly, and the reaction steps were the same as in Example 1.

[0395] Table 6. Product yields under different reaction conditions

[0396] Ionic nitrogen heterocyclic carbene ligands Cobalt catalyst alkali Yield (%) CNC-Me Cobalt acetylacetonate (II) / No product CNC-Me / Potassium tert-butoxide No product / Cobalt acetylacetonate (II) Potassium tert-butoxide No product CNC-Me / / No product / Cobalt acetylacetonate (II) / No product / / Potassium tert-butoxide No product

[0397] Note: " / " in the table indicates that the substance is not added.

[0398] Table 6 shows the product yields under different reaction conditions. As can be seen from Table 6, the preparation method of alkenyl geminoboronic esters provided by this invention requires the ionic nitrogen-heterocyclic carbene ligand, cobalt catalyst, and base. Specifically, the ionic nitrogen-heterocyclic carbene ligand is deprotonated under the action of a base to form a carbene active ligand, which coordinates with cobalt to obtain a cobalt complex. The cobalt complex is reduced by bipinacolboronic ester to obtain a cobalt catalyst active intermediate. This cobalt active catalyst reacts with an alkyne to obtain an alkynylcobalt active intermediate. Bipinacolboronic ester reacts with alkynylcobalt to obtain a cobalt-boron compound coordinated with pinacol-alkynyl. An in-situ insertion reaction forms styrene substituted with bipinacolboronic ester, which simultaneously reacts with another molecule of alkyne to regenerate the alkynylcobalt active intermediate.

[0399] As can be clearly seen from all the above embodiments, when the preparation method provided by the present invention is adopted, using cobalt compounds as catalysts (especially cobalt acetylacetonate) and ligands (especially CNC-Me and CNC-...), the results are satisfactory. i When a reaction system consisting of Pr, boron reagents (especially pinnatrol borate), bases (especially potassium tert-butoxide), and suitable organic solvents (especially DMF and THF) is used, different alkynes can undergo selective diboration to obtain the corresponding alkenyl geminiborates, providing an efficient synthetic route for the rapid synthesis of alkenylborates.

Claims

1. A method for preparing an alkenyl geminoboronate, characterized in that, Includes the following steps: Under an inert atmosphere, compound (a) is made The reaction occurs under the action of a cobalt catalyst, an ionic nitrogen heterocyclic carbene ligand, a boron reagent, and a base. The alkenyl geminosine ester shown in formula (A) is obtained. in: The cationic moiety of the ionic nitrogen heterocyclic carbene ligand is shown in formula (b): The anionic portion of the ionic nitrogen heterocyclic carbene ligand is selected from at least one of halide ions, tetrafluoroborate ions, hexafluorophosphate ions, trifluoromethanesulfonate ions, acetate ions, nitrate ions, and perchlorate ions; In formulas (a) and (A), R1 is selected from hydrogen, heterocycles, substituted or unsubstituted aryl groups, and substituted or unsubstituted hydrocarbon groups; In equation (b), R2 and R3 are each independently selected from C. 1-4 Alkyl group; R4, R5 and R6 are each independently selected from H or C. 1-4 alkyl.

2. The preparation method according to claim 1, characterized in that, The amount of the cobalt catalyst used is 0.1%-10% of the molar amount of the compound of formula (a); And / or, the amount of the ionic nitrogen heterocyclic carbene ligand is 0.14%-14% of the molar amount of the compound of formula (a); And / or, the molar ratio of the boron reagent to the compound of formula (a) is (1-3):1; And / or, the molar ratio of the base to the ionic nitrogen heterocyclic carbene ligand is (3-5):

1.

3. The preparation method according to claim 2, characterized in that, The cobalt catalyst is selected from monovalent cobalt compounds or divalent cobalt compounds.

4. The preparation method according to claim 2, characterized in that, The boron reagent is selected from at least one of pinacol diborate and neopentyl diborate.

5. The preparation method according to claim 2, characterized in that, The base is selected from at least one of nitrogen-containing organic bases with lone pairs of electrons and strong basic metal salts.

6. The preparation method according to claim 1, characterized in that, The reaction further includes the use of a solvent with a concentration of 0.1-0.3 mol / L; the ratio of the compound of formula (a) to the solvent is (0.1-1) mol: 1 mL.

7. The preparation method according to claim 1, characterized in that, The reaction is carried out at a temperature of 20-300℃ for a time of 0.1-48h.

8. An alkenyl geminosine ester, characterized in that, Including those prepared by the method described in any one of claims 1-7, the structural formula of which is shown in formula (A). Wherein, R1 is selected from hydrogen, heterocyclic, substituted or unsubstituted aryl, substituted or unsubstituted hydrocarbon groups.

9. The alkenyl geminoboronic acid ester according to claim 8, characterized in that, The alkenyl geminoboronic esters are shown in Formulas 1-34:

10. The use of the alkenyl geminoboronic acid ester according to claim 8 or 9 in the synthesis of polysubstituted olefins, natural products or pharmaceutical molecules.

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