Preparation method of alkenyl substituted α-hydroxyboric acid ester compound

Abstract

The present application relates to the technical field of synthetic chemistry, and in particular to a method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, comprising the following steps: subjecting an α, β-unsaturated alkynyl ketone compound shown in formula I and a pinacol borane shown in formula II to a hydroboration reaction under catalyst conditions to obtain an alkenyl-substituted α-hydroxyboric acid ester compound shown in formula III; the preparation method has the characteristics of single-minded reaction selectivity, few side reactions, and high efficiency, and has high application value in the field of synthetic chemistry.

Description

Technical Field

[0001] The present application belongs to the technical field of synthetic chemistry, and in particular relates to a method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound. Background Art

[0002] In alkenyl-substituted-α-hydroxyboric acid ester compounds, three different functional groups (alkenyl, hydroxyl and borate) are simultaneously connected to the same carbon atom. Therefore, this type of compound is considered to be a special type of allyl alcohol or allyl borate or α-hydroxyboric acid ester compound. Based on the functional group diversity of alkenyl-substituted-α-hydroxyboric acid ester compounds and the known synthetic chemical transformation patterns, they have high application potential and value in synthetic chemistry.

[0003] However, the current synthesis methods of such alkenyl-substituted α-hydroxyboronic acid ester compounds are relatively complicated, and there are great challenges in controlling the regioselectivity and stereoselectivity during the synthesis process. Therefore, it is necessary to develop a method with relatively simple process that can quickly prepare such compounds. Summary of the invention

[0004] The purpose of this application is to provide a method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, aiming to solve the technical problem of how to simply, quickly and efficiently prepare an alkenyl-substituted α-hydroxyboric acid ester compound. To achieve the above application purpose, the technical solution adopted in this application is as follows:

[0005] The present application provides a method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, comprising the following steps:

[0006] The α,β-unsaturated alkynone compound of formula I and the pinacol borane of formula II are subjected to a hydroboration reaction under a catalyst condition to obtain an alkenyl-substituted-α-hydroxyboric acid ester compound of formula III;

[0007]

[0008] Among them, R 1 Selected from C1-C 20 Alkyl, C1-C 20 Heteroalkyl, C3-C 20 Cycloalkyl, C3-C 20 Heterocycloalkyl, C1-C 20 Alkyloxycarbonyl (C1-C 20 ) alkyl, C1-C 20 Alkyloxycarbonyl (C1-C 20 ) heteroalkyl, C1-C 20 Alkyloxycarbonyl (C3-C 20 ) cycloalkyl, C1-C20 Alkyloxycarbonyl (C3-C 20 ) any one of heterocycloalkyl;

[0009] R 2 Selected from C1-C 20 Alkyl, C1-C 20 Heteroalkyl, C3-C 20 Cycloalkyl, C3-C 20 Heterocycloalkyl, C1-C 20 Alkyloxycarbonyl (C1-C 20 ) alkyl, C1-C 20 Alkyloxycarbonyl (C1-C 20 ) heteroalkyl, C1-C 20 Alkyloxycarbonyl (C3-C 20 ) cycloalkyl, C1-C 20 Alkyloxycarbonyl (C3-C 20 ) heterocycloalkyl, aromatic, heteroaromatic, substituted aromatic, aromatic (C1-C 20 ) alkyl, aromatic oxygen (C1-C 20 ) alkyl, sulfonyloxy (C1-C 20 ) alkyl, ester group (C1-C 20 ) alkyl, cyano (C1-C 20 ) alkyl, halogen (C1-C 20 ) alkyl, hydroxyl (C1-C 20 ) alkyl.

[0010] The preparation method of the alkenyl-substituted-α-hydroxyboric acid ester compound provided in the present application starts from a simple and readily available α,β-unsaturated alkynone compound, and can quickly and effectively achieve the preparation of the alkenyl-substituted-α-hydroxyboric acid ester compound through two consecutive highly selective hydroboration reactions under mild conditions. The preparation method has the characteristics of specific reaction selectivity, few side reactions, and high efficiency, and has high application value in the field of synthetic chemistry. DETAILED DESCRIPTION

[0011] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0012] The compounds and their derivatives involved in the embodiments of the present invention are named according to the IUPAC (International Union of Pure and Applied Chemistry) or CAS (Chemical Abstracts Service, located in Columbus, Ohio) naming system. Therefore, the compound groups specifically involved in the embodiments of the present invention are described and explained as follows: "Alkyl" refers to a straight chain or branched saturated fatty chain, including but not limited to methyl, ethyl, propyl such as isopropyl, butyl such as isobutyl, pentyl such as isopentyl, hexyl and other similar groups. "Heteroalkyl" refers to a straight chain or branched saturated fatty chain containing at least one heteroatom, wherein at least one carbon atom has been replaced by a heteroatom such as nitrogen, oxygen or sulfur, such as but not limited to methylaminoethyl, propyloxyethyl and other similar groups. "Cycloalkyl" refers to a saturated monocyclic or polycyclic alkyl, including but not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and other similar groups. "Heterocycloalkyl" refers to a saturated monocyclic or polycyclic alkyl, wherein at least one carbon atom has been replaced by a heteroatom such as nitrogen, oxygen or sulfur. "Aromatic" refers to a cyclic aromatic hydrocarbon, including monocyclic, polycyclic or condensed aromatic hydrocarbons, such as, but not limited to, phenyl, naphthyl, anthracenyl, phenanthrenyl and other similar groups. "Heteroaryl" refers to a monocyclic, polycyclic or condensed aromatic hydrocarbon in which one or more carbon atoms have been replaced by heteroatoms such as nitrogen, oxygen or sulfur. If a heteroaryl contains more than one heteroatom, these heteroatoms may be the same or different. Heteroaryl groups include, but are not limited to, benzofuranyl, benzothiophenyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, benzopyranyl, furanyl, imidazolyl, indazolyl, indolizinyl, indolyl, isobenzofuranyl, isoindolyl, isoquinolyl, isothiazolyl, isoxazolyl, naphthyridinyl, oxadiazolyl, oxazinyl, oxazolyl, phthalazinyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolyl, pyridinyl, pyrimidinyl, pyrrolyl, quinolizinyl, quinolyl, quinoxalinyl, thiadiazolyl, thiatriazolyl, thiazolyl, thienyl, triazinyl and other similar groups.

[0013] The present application provides a method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, comprising the following steps: subjecting an α,β-unsaturated alkynyl ketone compound shown in formula I and a pinacol borane shown in formula II to a hydroboration reaction under a catalyst condition to obtain an alkenyl-substituted α-hydroxyboric acid ester compound shown in formula III;

[0014]

[0015] Among them, R 1 Selected from C1-C 20 Alkyl, C1-C 20 Heteroalkyl, C3-C 20 Cycloalkyl, C3-C 20 Heterocycloalkyl, C1-C 20Alkyloxycarbonyl (C1-C 20 ) alkyl, C1-C 20 Alkyloxycarbonyl (C1-C 20 ) heteroalkyl, C1-C 20 Alkyloxycarbonyl (C3-C 20 ) cycloalkyl, C1-C 20 Alkyloxycarbonyl (C3-C 20 ) any one of heterocycloalkyl; R 2 Selected from C1-C 20 Alkyl, C1-C 20 Heteroalkyl, C3-C 20 Cycloalkyl, C3-C 20 Heterocycloalkyl, C1-C 20 Alkyloxycarbonyl (C1-C 20 ) alkyl, C1-C 20 Alkyloxycarbonyl (C1-C 20 ) heteroalkyl, C1-C 20 Alkyloxycarbonyl (C3-C 20 ) cycloalkyl, C1-C 20 Alkyloxycarbonyl (C3-C 20 ) heterocycloalkyl, aromatic, heteroaromatic, substituted aromatic, aromatic (C1-C 20 ) alkyl, aromatic oxygen (C1-C 20 ) alkyl, sulfonyloxy (C1-C 20 ) alkyl, ester group (C1-C 20 ) alkyl, cyano (C1-C 20 ) alkyl, halogen (C1-C 20 ) alkyl, hydroxyl (C1-C 20 ) alkyl.

[0016] α,β-Unsaturated alkynone compounds are a type of simple and easily available basic reaction modules. The present application embodiment uses such α,β-unsaturated alkynone compounds and pinacol borane as raw materials, and may prepare alkenyl-substituted-α-hydroxyboronic acid compounds through two consecutive hydroboration reactions of α,β-unsaturated alkynone compounds. Taking the catalyst as a ruthenium catalyst as an example, the reaction principle is as follows:

[0017]

[0018] Wherein, [Ru] is a metal catalyst, R 1 , R 2is the above-mentioned selectable group. In the above process: α,β-unsaturated alkynone and pinacol borane undergo a hydroboration reaction similar to a 1,4-conjugated addition reaction to generate an allene intermediate as shown in formula IV. The first hydroboration reaction may have a potential competitive reaction, and the present application generates the allene intermediate by controlling the chemical selectivity. In the second hydroboration reaction, the allene intermediate as shown in formula IV undergoes a hydroboration reaction to generate an intermediate as shown in formula V. The process involves the control of both regioselectivity and stereoselectivity. The present application finally obtains an alkenyl-substituted-α-hydroxyboric acid ester compound as shown in formula III through unique reaction activity, chemical selectivity, regioselectivity and stereoselectivity control. The preparation method has the characteristics of specific reaction selectivity, few side reactions and high efficiency, and has high application value in the field of synthetic chemistry.

[0019] In the above preparation method, R 1 and R 2 Corresponding to R in the alkenyl-substituted α-hydroxyboronic acid ester compound shown in Formula III 1 and R 2 .

[0020] When R 1 or R 2 Selected from C1-C 20 In the case of an alkyl group (i.e., having 1 to 20 carbon atoms), in one embodiment, the C1-C 20 The alkyl group can be C1-C 15 Alkyl, C1-C 10 Alkyl, C1-C5 alkyl, C1-C3 alkyl, etc. In some embodiments, it can be methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, etc.

[0021] When R 1 or R 2 Selected from C1-C 20 In one embodiment, the C1-C 20 The heteroalkyl group can be C1-C 15 Heteroalkyl, C1-C 10 In some embodiments, the heteroatom may be a C-C heteroalkyl group, a C2-C8 heteroalkyl group, a C3-C4 heteroalkyl group, etc. ...

[0022] When R 1 or R 2 Selected from C3-C 20 In one embodiment, the C3-C 20 The cycloalkyl group may be C3-C 15 Cycloalkyl, C3-C 10Cycloalkyl, C3-C4 cycloalkyl, etc. In certain embodiments, the cycloalkyl can be cyclopropyl, cyclobutyl, cyclopentyl, etc.

[0023] When R 1 or R 2 Selected from C3-C 20 In one embodiment, the C3-C 20 The heterocycloalkyl group may be C3-C 15 Heterocycloalkyl, C3-C 10 In some embodiments, the heteroatom may be an oxygen atom, a nitrogen atom, a sulfur atom, or the like.

[0024] When R 1 or R 2 Selected from C1-C 20 Alkyloxycarbonyl (C1-C 20 ) alkyl, in one embodiment, the C1-C 20 Alkyloxycarbonyl (C1-C 20 ) The alkyl group may be (C1-C 10 )alkyloxycarbonyl (C1-C 20 )alkyl, (C1-C8)alkyloxycarbonyl(C1-C8)alkyl, (C1-C4)alkyloxycarbonyl(C1-C4)alkyl, etc. In some embodiments, it can be but not limited to methyloxycarbonylethyl, ethyloxycarbonylbutyl, propyloxycarbonylbutyl, etc.

[0025] When R 1 or R 2 Selected from C1-C 20 Alkyloxycarbonyl (C1-C 20 ) heteroalkyl, in one embodiment, the C1-C 20 Alkyloxycarbonyl (C1-C 20 ) heteroalkyl can be (C1-C 10 )alkyloxycarbonyl (C1-C 10 )heteroalkyl, (C1-C8)alkyloxycarbonyl(C1-C8)heteroalkyl, (C1-C4)alkyloxycarbonyl(C1-C4)heteroalkyl, etc. In certain embodiments, the heteroatom may be an oxygen atom, a nitrogen atom, a sulfur atom, etc.

[0026] When R 1 or R 2 Selected from C1-C 20 Alkyloxycarbonyl (C3-C 20 ) cycloalkyl, in one embodiment, the C1-C 20 Alkyloxycarbonyl (C3-C 20 ) Cycloalkyl can be (C1-C 10 )alkyloxycarbonyl (C3-C10 )cycloalkyl, (C1-C8)alkyloxycarbonyl(C3-C8)cycloalkyl, (C1-C4)alkyloxycarbonyl(C3-C4)cycloalkyl, etc. In certain embodiments, it can be, but is not limited to, methyloxycarbonylcyclopropyl, ethyloxycarbonylcyclobutyl, propyloxycarbonylcyclobutyl, butyloxycarbonylcyclopentyl, etc.

[0027] When R 1 or R 2 Selected from C1-C 20 Alkyloxycarbonyl (C3-C 20 ) heterocycloalkyl, in one embodiment, the C1-C 20 Alkyloxycarbonyl (C3-C 20 )Heterocycloalkyl may be (C1-C 10 )alkyloxycarbonyl (C3-C 10 )heterocycloalkyl, (C1-C8)alkyloxycarbonyl(C3-C8)heterocycloalkyl, (C1-C4)alkyloxycarbonyl(C3-C4)heterocycloalkyl, etc. In certain embodiments, the heteroatom may be an oxygen atom, a nitrogen atom, a sulfur atom, etc.

[0028] When R 2 When selected from aromatic groups, in one embodiment, the aromatic group can be, but is not limited to, a monocyclic aromatic group, a polycyclic aromatic group, or a condensed aromatic group. In one embodiment, the aromatic group is a monocyclic aromatic group. In certain embodiments, the aromatic group can be C6-C 14 Aromatic groups, such as phenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl, etc.

[0029] When R 2 When selected from heteroaromatic groups, in one embodiment, the heteroaromatic group may be C4-C 14 Heteroaryl, such as thienyl, thiazolyl, pyrrolyl, pyrazinyl, pyridinyl, benzothiophene and the like.

[0030] When R 2 When selected from substituted aromatic groups, the substituted aromatic groups may be, but are not limited to, single or multiple substituted aromatic groups at the ortho, meta, or para positions. Specifically, the substituents are selected from halogen (F, Cl, Br, I, etc.), C1-C 10 Alkyl, halogenated C1-C 10 At least one of the alkyl groups, for example, the phenyl group of the above substituents.

[0031] When R 2 Selected from aromatic groups (C1-C 20 ) alkyl, in one embodiment, the aromatic group (C1-C 20 ) The alkyl group may be C6-C 14 Aromatic (C1-C 10 ) alkyl, such as phenyl (C1-C 10) alkyl, phenyl (C1-C5) alkyl, phenyl (C1-C4) alkyl, phenyl (C1-C3) alkyl, etc. In certain embodiments, aromatic (C1-C 20 ) The alkyl group may be phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, or the like.

[0032] When R 2 Selected from aromatic oxygen (C1-C 20 ) alkyl, in one embodiment, the aromatic oxygen (C1-C 20 ) The alkyl group may be C6-C 14 Aromatic oxygen (C1-C 10 ) alkyl, such as phenyloxy (C1-C 10 )alkyl, phenyloxy(C1-C5)alkyl, etc. For example, phenyloxymethyl, phenyloxyethyl, phenyloxypropyl, phenyloxybutyl, etc. may be mentioned.

[0033] When R 2 Selected from sulfonyloxy (C1-C 20 )alkyl, in one embodiment, the sulfonyloxy (C1-C 20 ) The alkyl group may be C4-C 14 Sulfonyloxy (C1-C 10 ) alkyl, such as tosyloxy (C1-C 10 )alkyl, tosyloxy (C1-C5)alkyl, etc. 2 Selected from ester groups (C1-C 20 ) alkyl, in one embodiment, the ester group (C1-C 20 ) The alkyl group may be C1-C 10 Ester group (C1-C 10 ) alkyl, such as butyl ethyl, propyl ethyl, etc.

[0034] When R 2 Selected from cyano (C1-C 20 )alkyl, in one embodiment, the cyano group (C1-C 20 ) The alkyl group may be a cyano group (C1-C 10 ) alkyl, such as cyanoethyl, cyanopropyl, cyanobutyl, etc. 2 Selected from halogen (C1-C 20 ) alkyl, in one embodiment, the halogen (C1-C 20 ) The alkyl group may be a halogen group (C1-C 10 ) alkyl, such as haloethyl, halopropyl, halobutyl, etc., and the halo group can be fluorine, chlorine, bromine, iodine, etc. When R 2 Selected from hydroxyl (C1-C 20 ) alkyl, in one embodiment, the hydroxyl group (C1-C 20 ) The alkyl group may be a hydroxyl group (C1-C10 ) alkyl, such as hydroxyethyl, hydroxypropyl, hydroxybutyl, etc.

[0035] In one embodiment, the catalyst is selected from a ruthenium metal catalyst, which can catalyze the hydroboration reaction of α,β-unsaturated alkynone compounds with pinacol borane with high efficiency and selectivity. Specifically, the ruthenium metal catalyst is selected from [Cp*Ru(MeCN)3]PF6, [CpRu(MeCN)3]PF6, [Cp*RuCl]4 and [Cp*RuCl2] n At least one of them, and preferably, [Cp*Ru(MeCN)3]PF6 exhibits the best catalytic performance. Further, the amount of the catalyst added is 2.5% to 10% of the molar amount of the α,β-unsaturated alkynyl ketone compound. At this molar ratio, the metal catalyst can achieve an efficient catalytic hydroboration reaction of the α,β-unsaturated alkynyl ketone compound.

[0036] In one embodiment, the amount of pinacol borane added is 2 to 3 times the molar amount of α, β-unsaturated alkynone, for example, it can be 220% of the molar amount of α, β-unsaturated alkynone. The amount of pinacol borane added can ensure the efficient progress of the catalytic reaction and reduce the waste of borane raw materials. With the above amount of addition, the α, β-unsaturated alkynone compound can fully undergo hydroboration reaction to obtain the product efficiently and in high yield.

[0037] In one embodiment, the hydroboration reaction is carried out in an organic solvent, and the organic solvent is selected from at least one of dichloroethane, dichloromethane, chloroform, ethyl acetate, and acetonitrile. The temperature of the hydroboration reaction is 20 to 40°C. Specifically, after dissolving the α,β-unsaturated alkynyl ketone shown in formula I and the pinacol borane shown in formula II in the above organic solvent, a metal catalyst is added, and the hydroboration reaction of the alkynyl ketone is carried out under the above mild conditions, so that the alkenyl substituted-α-hydroxyboric acid ester compound shown in III can be efficiently and quickly synthesized.

[0038] In one embodiment, the hydroboration reaction is carried out in a protective atmosphere, and the gas of the protective atmosphere is selected from at least one of nitrogen, argon, and helium. In this way, the reaction can be carried out stably. Finally, after the reaction is completed, triethylamine can be added to quench the reaction, and then the reaction solution is filtered through a short silica gel column to obtain a high-purity alkenyl-substituted-α-hydroxyboric acid ester compound represented by formula III.

[0039] The following describes the invention in conjunction with specific embodiments.

[0040] Example 1

[0041]

[0042] A method for preparing an alkenyl-substituted α-hydroxyboronic acid ester compound, using R 1isopropyl, R 2 α,β-unsaturated alkynone (2-methyltridec-4-yn-3-one) of n-octyl alkynone and pinacol borane (HBpin) are used as reaction raw materials, and [Cp*Ru(MeCN)3]PF6 catalyst is used for reaction. The specific implementation process includes: under nitrogen protection, 104mg alkynone (0.50mmol), 141mg pinacol borane (HBpin) and 2.5mL dichloroethane solvent are added to a 4mL dry bottle, and then 6.3mg [Cp*Ru(MeCN)3]PF6 (2.5mol%) is added. The reaction is carried out at room temperature (25-27℃) for 6 hours. The reaction equation is as above. After the reaction is completed, 75mg triethylamine is added to quench the reaction, and then the reaction solution is filtered through a short silica gel, eluted with ether, concentrated and chromatographed on a silica gel column to obtain 128mg of a colorless oily liquid product, with a calculated yield of 76%. The obtained reaction products were analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry. The test results are as follows:

[0043] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0044] 1 H NMR (400MHz, CDCl3) δ5.60(dt,J=15.5,6.8Hz,1H),5.42(dt,J=15.5,1.2Hz,1H),2.01(q,J=6.8Hz,2 H),1.83–1.76(m,1H),1.60(s,1H),1.32–1.21(m,24H),0.93(d,J=6.8Hz,3H),0.85–0.79(m,6H)ppm.

[0045] 13 C NMR (100MHz, CDCl3) δ133.8,128.4,84.1,71.6,35.0,32.4,31.8,29.5,29.4,29.3,29.0,24.5,22.6,18.7,15.4,14.0.

[0046] Infrared spectrum: IR (thin film) 3611, 2965, 2924, 2858, 1460, 1375, 1321, 1261, 1219, 1138cm -1 .

[0047] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 20 H 39 BNaO3[M+Na] + :361.2884,found:361.2891.

[0048] From the result, it can be seen that its theoretical mass is 361.2884, while the observed value of the peak found in the actual mass spectrum is 361.2891; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0049] Example 2

[0050]

[0051] A method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, as shown in the above reaction equation, uses 76 mg of alkynone (2-methylnon-4-yn-3-one) and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, and follows the same steps as Example 1, using 2.5 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, a colorless oily liquid of 101 mg, with a calculated yield of 72%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0052] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0053] 1 H NMR(400MHz, CDCl3)δ5.60(dt,J=15.6,6.8Hz,1H),5.42(dt,J=15.6,1.3Hz,1H),2.03–1.98(m,2 H), 1.83–1.76 (m, 1H), 1.59 (s, 1H), 1.32–1.21 (m, 16H), 0.93 (d, J = 6.8Hz, 3H), 0.85–0.79 (m, 6H).

[0054] 13 C NMR (100MHz, CDCl3) δ133.8,128.3,84.1,71.4,34.9,32.0,31.6,24.5,21.9,18.7,15.4,13.8.

[0055] Infrared spectrum: IR (thin film) 2958, 2925, 1462, 1375, 1321, 1263, 1213, 1139cm -1 .

[0056] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 16 H 30 BO3[M–H] – :281.2293,found:281.2286.

[0057] From the result, it can be seen that its theoretical mass is 281.2293, while the observed value of the peak found in the actual mass spectrum is 281.2286; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0058] Example 3

[0059]

[0060] A method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, as shown in the above reaction equation, uses 77 mg of alkynone (7-methoxy-2-methylhept-4-yn-3-one) and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, follows the same steps as in Example 1, uses 2.5 mol% of ruthenium catalyst, reacts for 6 hours, and obtains the corresponding reaction product, 98 mg of colorless oily liquid, with a calculated yield of 69%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0061] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0062] 1 H NMR(400MHz, CDCl3)δ5.61(dt,J=15.5,6.6Hz,1H),5.55–5.47(m,1H),3.34(t,J=7.0Hz,2H),3.27(s,3H),2.2 9(q,J=7.0Hz,2H),1.85–1.72(m,1H),1.66(s,1H),1.20(s,12H),0.92(d,J=6.8Hz,3H),0.79(d,J=6.9Hz,3H).

[0063] 13 C NMR (100MHz, CDCl3) δ135.9,124.1,84.1,72.5,71.8,58.3,34.9,32.7,24.5,18.6,15.4.

[0064] Infrared spectrum: IR (thin film) 3386, 2974, 2932, 2875, 1697, 1671, 1629, 1515, 1451, 1376, 1334, 1215, 1143, 1114, 1010cm -1 .

[0065] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 15 H 29BNaO4[M+Na] + :307.2054,found:307.2051.

[0066] From the result, it can be seen that its theoretical mass is 307.2054, while the observed value of the peak found in the actual mass spectrum is 307.2051; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0067] Example 4

[0068]

[0069] Preparation of an alkenyl-substituted α-hydroxyboronic acid ester compound, as shown in the above reaction equation, using 127 mg of alkynone (7-((tert-butyldimethylsilyl)oxy)-2-methylhept-4-yn-3-one) and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, following the same steps as in Example 1, using 2.5 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, a colorless oily liquid of 155 mg, with a calculated yield of 81%. The obtained reaction product was analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis was as follows:

[0070] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0071] 1 H NMR (400MHz, CDCl3) δ5.60(dt,J=15.5,6.7Hz,1H),5.48(d,J=15.6Hz,1H),3.55(t,J=7.0Hz,2H),2.22(q,J=6.8Hz,2H) ,1.81–1.74(m,1H),1.60(s,1H),1.19(s,12H),0.90(d,J=6.8Hz,3H),0.82(s,9H),0.78(d,J=6.9Hz,3H),-0.02(s,6H).

[0072] 13 C NMR (100MHz, CDCl3) δ135.8,124.3,84.1,71.6,63.3,36.2,34.9,25.8,24.5,18.6,18.2,15.4,–5.4.

[0073] Infrared spectrum: IR (thin film) 3611, 2955, 2935, 2893, 2861, 1466, 1375, 1322, 1255, 1214, 1137, 1097cm -1 .

[0074] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 20 H 41 BNaO4Si[M+Na] + :407.2759,found:407.2762.

[0075] From the result, it can be seen that its theoretical mass is 407.2759, while the observed value of the peak found in the actual mass spectrum is 407.2762; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0076] Example 5

[0077]

[0078] A preparation of an alkenyl substituted-α-hydroxyboronic acid ester compound, as shown in the above reaction equation, using 112 mg of alkynone (2-methyl-7-((tetrahydro-2H-pyran-2-yl)oxy)hept-4-yn-3-one) and 141 mg of pinacol borane corresponding to the equation as reaction raw materials, following the same steps as in Example 1, using 2.5 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, a colorless oily liquid of 131 mg, with a calculated yield of 74%. The obtained reaction product was analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis was as follows:

[0079] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0080] 1 H NMR (400MHz, CDCl3) δ5.60 (dt, J=15.5, 6.7Hz, 1H), 5.48 (d, J=15.6Hz, 1H), 4. 52–4.50(m,1H),3.80–3.75(m,1H),3.69–3.63(m,1H),3.42–3.38(m,1H),3.3 6–3.30(m,1H),2.27(q,J=6.9Hz,2H),1.78–1.70(m,2H),1.64–1.58(m,2H),1 .50–1.41(m,4H),1.16(s,12H),0.89(d,J=6.8Hz,3H),0.75(d,J=6.8Hz,3H).

[0081] 13C NMR (100MHz, CDCl3) δ135.7,124.2,98.4,84.0,71.6,67.1,61.9,34.9,32.8,30.5,25.3,24.4,19.3,18.5,15.4.

[0082] Infrared spectrum: IR (thin film) 3605, 3469, 2942, 2870, 1456, 1375, 1321, 1262, 1207, 1132, 1070, 1028cm -1 .

[0083] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 19 H 35 BNaO5[M+Na] + :377.2470,found:377.2480.

[0084] From the result, it can be seen that its theoretical mass is 377.2470, while the observed value of the peak found in the actual mass spectrum is 377.2480; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0085] Example 6

[0086]

[0087] A method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, as shown in the above reaction equation, this embodiment uses 112 mg of 6-methyl-5-oxohept-3-yn-1-yl pivalate and 141 mg of HBpin corresponding to the above equation as reaction raw materials, and follows the same steps as in Example 1, using 2.5 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, a colorless oily liquid of 114 mg, with a calculated yield of 64%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0088] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0089] 1H NMR (400MHz, CDCl3) δ5.59(dt,J=15.5,6.2Hz,1H),5.52(d,J=15.7Hz,1H),3.99(t,J=6.8Hz,2H),2.31(q,J=6.6 Hz,2H),1.79–1.72(m,1H),1.66(s,1H),1.17(s,12H),1.11(s,9H),0.89(d,J=6.8Hz,3H),0.76(d,J=6.9Hz,3H).

[0090] 13 C NMR (100MHz, CDCl3) δ178.3,136.4,123.2,84.1,71.5,63.9,38.5,34.9,31.7,27.0,24.5,24.4,18.5,15.5.

[0091] Infrared spectrum: IR (thin film) 3653, 3612, 2970, 2876, 1726, 1471, 1373, 1322, 1281, 1214, 1143, 1036cm -1 .

[0092] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 19 H 35 BNaO5[M+Na] + :377.2470,found:377.2481.

[0093] From the result, it can be seen that its theoretical mass is 377.2470, while the observed value of the peak found in the actual mass spectrum is 377.2481; combined with nuclear magnetic resonance and infrared elemental analysis, it can be determined that the structure of the product is the product of this example.

[0094] Example 7

[0095]

[0096] A method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, as shown in the above reaction equation, this embodiment uses 123 mg of alkynone (8-methyl-7-oxonon-5-yn-1-yl methanesulfonate) and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, and follows the same steps as in Example 1, using 2.5 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, a colorless oily liquid of 163 mg, with a calculated yield of 87%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0097] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0098] 1 H NMR (400MHz, CDCl3) δ5.51(dt,J=15.4,6.7Hz,1H),5.38(d,J=15.6Hz,1H),4.09(t,J=6.5Hz,2H),2.88(s,3H),2.00(q ,J=7.0Hz,2H),1.73–1.61(m,4H),1.41–1.35(m,2H),1.15–1.10(m,12H),0.84(d,J=6.8Hz,3H),0.71(d,J=6.8Hz,3H).

[0099] 13 C NMR (100MHz, CDCl3) δ134.6,126.8,84.0,71.2,69.7,36.9,34.7,31.4,28.1,24.9,24.5,24.2,18.4,15.3.

[0100] Infrared spectrum: IR (thin film) 3551, 2974, 2938, 2873, 1461, 1449, 1330, 1263, 1215, 1170, 1139cm -1 .

[0101] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 17 H 33 BNaO6S[M+Na] + :399.1983,found:399.1981.

[0102] From the result, it can be seen that its theoretical mass is 399.1983, while the observed value of the peak found in the actual mass spectrum is 399.1981; combined with nuclear magnetic resonance and infrared elemental analysis, it can be determined that the structure of the product is the product of this example.

[0103] Example 8

[0104]

[0105] A preparation of an alkenyl substituted-α-hydroxyboric acid ester compound, as shown in the above reaction equation, using 142 mg of alkynone (2-(7-methyl-6-oxooct-4-yn-1-yl)isoindoline-1,3-dione) and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, following the same steps as in Example 1, using 2.5 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, a colorless oily liquid of 145 mg, with a calculated yield of 70%. The obtained reaction product was analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis was as follows:

[0106] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0107] 1 H NMR (400MHz, CDCl3) δ7.80–7.69(m,2H),7.68–7.58(m,2H),5.60(dt,J=15.5,6.6Hz,1H),5.46(d,J=15.6Hz,1H),3.60(t, J=7.3Hz,2H),2.04(dd,J=14.4,7.1Hz,2H),1.85–1.58(m,4H),1.17(s,12H),0.89(d,J=6.8Hz,3H),0.76(d,J=6.8Hz,3H).

[0108] 13 C NMR (100MHz, CDCl3) δ168.1,134.8,133.6,131.9,126.4,122.9,84.0,71.4,37.5,34.9,29.7,28.3,24.5,24.4,18.5,15.4.

[0109] Infrared spectrum: IR (thin film) 3602, 3533, 3475, 2976, 2939, 2872, 1772, 1709, 1618, 1441, 1386, 1366, 1323, 1262, 1137, 1075, 1037cm -1 .

[0110] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 23 H 32 BNNaO[M+Na] + :436.2266,found:436.2274.

[0111] From the result, it can be seen that its theoretical mass is 436.2266, while the observed value of the peak found in the actual mass spectrum is 436.2274; combined with nuclear magnetic resonance and infrared elemental analysis, it can be determined that the structure of the product is the product of this example.

[0112] Example 9

[0113]

[0114] A method for preparing an alkenyl-substituted α-hydroxyboronic acid ester compound, as shown in the above reaction equation, uses 82 mg of alkynone (8-methyl-7-oxonon-5-ynenitrile) and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, follows the same steps as in Example 1, uses 2.5 mol% of ruthenium catalyst, reacts for 6 hours, and obtains the corresponding reaction product, 118 mg of colorless oily liquid, with a calculated yield of 81%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0115] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0116] 1 H NMR (400MHz, CDCl3) δ5.57–5.47(m,2H),2.25(t,J=7.2Hz,2H),2.17–2.12(m,2H),1.81–1.74(m, 1H),1.72(s,1H),1.70–1.63(m,2H),1.18(s,12H),0.89(d,J=6.8Hz,3H),0.76(d,J=6.8Hz,3H).

[0117] 13 C NMR (100MHz, CDCl3) δ136.1,124.9,119.4,84.1,71.5,34.7,30.9,24.9,24.4,18.4,16.0,15.4.

[0118] Infrared spectrum: IR (thin film) 3602, 3539, 3506, 3462, 2972, 2247, 1631, 1456, 1376, 1323, 1262, 1216, 1135cm -1 .

[0119] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 16 H 28 BNNaO3[M+Na] +:316.2054,found:316.2066.

[0120] From the result, it can be seen that its theoretical mass is 316.2054, while the observed value of the peak found in the actual mass spectrum is 316.2066; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0121] Example 10

[0122]

[0123] A method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, as shown in the above reaction equation, this embodiment uses 86 mg of alkynone (8-chloro-2-methyloct-4-yn-3-one) and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, and follows the same steps as in Example 1, using 2.5 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, a colorless oily liquid of 119 mg, with a calculated yield of 79%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0124] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0125] 1 H NMR (400MHz, CDCl3) δ5.57(dt,J=15.4,6.4Hz,1H),5.49(d,J=15.6Hz,1H),3.47(t,J=6.7Hz,2H),2.16(q, J=6.8Hz,2H),1.83–1.75(m,3H),1.66(s,1H),1.20(s,12H),0.92(d,J=6.8Hz,3H),0.78(d,J=6.9Hz,3H).

[0126] 13 C NMR (100MHz, CDCl3) δ135.4,125.8,84.2,71.6,44.1,34.9,32.1,29.3,24.5,18.6,15.4.

[0127] Infrared spectrum: IR (thin film) 3594, 3465, 2969, 2876, 1453, 1374, 1322, 1261, 1136cm -1 .

[0128] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 15 H 28BClNaO3[M+Na] + :325.1712,found:325.1712.

[0129] From the result, it can be seen that its theoretical mass is 325.1712, while the observed value of the peak found in the actual mass spectrum is 325.1712; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0130] Embodiment 11

[0131]

[0132] A method for preparing an alkenyl-substituted α-hydroxyboronic acid ester compound, as shown in the above reaction equation, uses 173 mg of alkynone (8-bromo-2-methyloct-4-yn-3-one) and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, follows the same steps as in Example 1, uses 2.5 mol% of ruthenium catalyst, reacts for 6 hours, and obtains the corresponding reaction product, 131 mg of colorless oily liquid, with a calculated yield of 76%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0133] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0134] 1 H NMR (400MHz, CDCl3) δ5.60–5.48(m,2H),3.34(t,J=6.7Hz,2H),2.17(q,J=6.8Hz,2H),1. 90–1.76(m,3H),1.67(s,1H),1.20(s,12H),0.92(d,J=6.8Hz,3H),0.78(d,J=6.8Hz,3H).

[0135] 13 C NMR (100MHz, CDCl3) δ135.5,125.6,84.2,71.5,34.8,33.1,32.2,30.5,24.5,18.6,15.4.

[0136] Infrared spectrum: IR (thin film) 3605, 2972, 2871, 1375, 1322, 1262, 1135, 1072, 1037cm -1 .

[0137] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 15 H 28BBrNaO3[M+Na] + :369.1207,found:369.1214.

[0138] From the result, it can be seen that its theoretical mass is 369.1207, while the observed value of the peak found in the actual mass spectrum is 369.1214; combined with nuclear magnetic resonance and infrared elemental analysis, it can be determined that the structure of the product is the product implemented in this example.

[0139] Example 12

[0140]

[0141] A method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, as shown in the above reaction equation, this embodiment uses 70 mg of alkynone (7-hydroxy-2-methylhept-4-yn-3-one) and 205 mg of pinacol borane as reaction raw materials, and follows the same steps as in Example 1, using 2.5 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, a colorless oily liquid of 91 mg, with a calculated yield of 67%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0142] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0143] 1 H NMR (400MHz, CDCl3) δ5.66–5.56(m,2H),3.61–3.57(m,2H),2.30(q,J=6.2Hz,2H ),1.88–1.80(m,3H),1.22(s,12H),0.94(d,J=6.8Hz,3H),0.82(d,J=6.8Hz,3H).

[0144] 13 C NMR (100MHz, CDCl3) δ137.2,123.9,84.3,71.8,62.0,35.9,34.9,24.5,18.6,15.6.

[0145] Infrared spectrum: IR (thin film) 3400, 2971, 2934, 2875, 1461, 1375, 1321, 1264, 1220, 1137, 1046cm -1 .

[0146] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 14 H 27 BNaO4[M+Na]+ :293.1895,found:293.1904.

[0147] From the result, it can be seen that its theoretical mass is 293.1895, while the observed value of the peak found in the actual mass spectrum is 293.1904; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0148] Example 12

[0149]

[0150] A method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, as shown in the above reaction equation, this embodiment uses 84 mg of alkynone (9-hydroxy-2-methylnon-4-yn-3-one) and 205 mg of pinacol borane corresponding to the above equation as reaction raw materials, and follows the same steps as in Example 1, using 2.5 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, a colorless oily liquid of 114 mg, with a calculated yield of 77%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0151] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0152] 1 H NMR (400MHz, CDCl3) δ5.62(dt,J=15.4,6.8Hz,1H),5.46(d,J=15.6Hz,1H),3.59(t,J=6.5Hz,2H),2.09–2.01(m,2H),1.86– 1.74(m,1H),1.67(m,2H),1.58–1.47(m,2H),1.45–1.37(m,2H),1.22(s,12H),0.94(d,J=6.8Hz,3H),0.81(d,J=6.8Hz,3H).

[0153] 13 C NMR (100MHz, CDCl3) δ134.2,127.9,84.2,74.9,62.7,35.0,32.12,32.10,25.6,24.6,24.55,24.53,18.7,15.6.

[0154] Infrared spectrum: IR (thin film) 3416, 2973, 2932, 2869, 1458, 1376, 1321, 1262, 1218, 1137, 1060cm -1 .

[0155] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 16 H 31 BNaO4[M+Na] + :321.2208,found:321.2218.

[0156] From the result, it can be seen that its theoretical mass is 321.2208, while the observed value of the peak found in the actual mass spectrum is 321.2218; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0157] Embodiment 13

[0158]

[0159] A method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, as shown in the above reaction equation, this embodiment uses 69 mg of alkynone (2,6-dimethylhept-4-yn-3-one) and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, and follows the same steps as in Example 1, using 2.5 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, a colorless oily liquid of 98 mg, with a calculated yield of 73%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0160] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0161] 1 H NMR(400MHz, CDCl3)δ5.60(dd,J=15.7,6.8Hz,1H),5.38(dd,J=15.7,1.1Hz,1H),2.32–2.23(m,1H) ,1.84–1.77(m,1H),1.59(s,1H),1.21(s,12H),0.94(dd,J=6.7,1.7Hz,9H),0.79(d,J=6.9Hz,3H).

[0162] 13 C NMR (100MHz, CDCl3) δ135.5,131.0,84.1,71.2,34.9,31.0,24.5,24.4,22.7,18.8,15.3.

[0163] Infrared spectrum: IR (thin film) 3612, 3563, 2962, 2873, 1462, 1374, 1320, 1261, 1139cm -1 .

[0164] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 15 H 29 BNaO3[M+Na] + :291.2102,found:291.2110.

[0165] From the result, it can be seen that its theoretical mass is 291.2102, while the observed value of the peak found in the actual mass spectrum is 291.2110; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0166] Embodiment 14

[0167]

[0168] A method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, as shown in the above reaction equation, this embodiment uses 82 mg of alkynone (1-cyclopentyl-4-methylpent-1-yn-3-one) and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, and follows the same steps as in Example 1, using 2.5 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, a colorless oily liquid of 105 mg, with a calculated yield of 71%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0169] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0170] 1 H NMR(400MHz, CDCl3)δ5.60(dd,J=15.6,7.5Hz,1H),5.40(dd,J=15.6,0.8Hz,1H),2.45–2.36(m,1H),1.82–1.75 (m,1H),1.73–1.64(m,2H),1.63–1.44(m,5H),1.28–1.17(m,14H),0.92(d,J=6.8Hz,3H),0.78(d,J=6.8Hz,3H).

[0171] 13 C NMR (100MHz, CDCl3) δ133.0,131.9,84,0,71.4,43.1,34.9,33.2,24.90,24.88,24.43,24.42,18.7,15.3.

[0172] Infrared spectrum: IR (thin film) 3610, 2951, 2869, 1458, 1374, 1319, 1262, 1136cm -1 .

[0173] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 17 H 31 BNaO3[M+Na] + :317.2258,found:317.2262.

[0174] From the result, it can be seen that its theoretical mass is 317.2258, while the observed value of the peak found in the actual mass spectrum is 317.2262; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0175] Embodiment 15

[0176]

[0177] A preparation of an alkenyl substituted α-hydroxyboronic acid ester compound, as shown in the above reaction equation, using 239 mg of tert-butyl 4-(undec-2-ynoyl)piperidine-1-carboxylate and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, following the same steps as in Example 1, using 2.5 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, a colorless oily liquid of 171 mg, with a calculated yield of 71%. The obtained reaction product was analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis was as follows:

[0178] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0179] 1 H NMR(400MHz, CDCl3) δ5.57(dt,J=15.4,6.8Hz,1H),5.35(d,J=15.6Hz,1H),4.03(s,2H),2 .54(s,2H),1.95(q,J=6.8Hz,2H),1.75(s,1H),1.59–1.09(m,38H),0.78(t,J=6.6Hz,3H).

[0180] 13C NMR (100MHz, CDCl3) δ154.5,132.6,129.0,84.2,78.8,70.4,43.6,32.2,31.7,29.3,29.2,29.1,28.8,28.2,27.8,25.0,24.4,22.4,13.9.

[0181] Infrared spectrum: IR (thin film) 2974, 2925, 2858, 1689, 1420, 1372, 1322, 1290, 1237, 1166, 1136, 1081, 1007cm -1 .

[0182] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 27 H 50 BNNaO5[M+Na] + :502.3674,found:502.3683.

[0183] From the result, it can be seen that its theoretical mass is 502.3674, while the observed value of the peak found in the actual mass spectrum is 502.3683; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0184] Example 16

[0185]

[0186] A method for preparing an alkenyl-substituted α-hydroxyboronic acid ester compound, as shown in the above reaction equation, uses 124 mg of alkynone (1-cyclohexylundec-2-yn-1-one) and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, follows the same steps as in Example 1, uses 2.5 mol% of ruthenium catalyst, reacts for 6 hours, and obtains the corresponding reaction product, a colorless oily liquid of 159 mg, with a calculated yield of 84%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0187] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0188] 1 H NMR (400MHz, CDCl3) δ5.58(dt,J=15.3,6.8Hz,1H),5.40(d,J=15.6Hz,1H),1.98(q,J=6.9Hz,2H),1.73–0.87(m,36H),0.81(t,J=6.8Hz,3H).

[0189] 13 C NMR (100MHz, CDCl3) δ133.7,128.3,84.2,71.7,45.4,32.5,31.9,29.6,29.5,29.4,29.2,29.1,26.8,26.6,25.7,24.6,22.7,14.1.

[0190] Infrared spectrum: IR (thin film) 3608, 2972, 2922, 2854, 1452, 1373, 1319, 1259, 1139, 1092cm -1 .

[0191] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 23 H 43 BNaO3[M+Na] + :401.3197,found:401.3207.

[0192] From the result, it can be seen that its theoretical mass is 401.3197, while the observed value of the peak found in the actual mass spectrum is 401.3207; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0193] Embodiment 17

[0194]

[0195] A method for preparing an alkenyl-substituted α-hydroxyboronic acid ester compound, as shown in the above reaction equation, this embodiment uses 111 mg of alkynone (2,2-dimethyltridec-4-yn-3-one) and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, and follows the same steps as in Example 1, using 2.5 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, a colorless oily liquid of 143 mg, with a calculated yield of 81%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0196] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0197] 1 H NMR (400MHz, CDCl3) δ5.67–5.58(m,2H),2.04–2.00(m,2H),1.86(s,1H),1.33–1.19(m,24H),0.92(s,9H),0.84(t,J=6.6Hz,3H).

[0198] 13 C NMR (100MHz, CDCl3) δ131.2,129.1,84.1,73.6,37.1,32.6,31.8,29.6,29.4,29.3,29.0,25.6,24.6,24.5,22.6,14.0.

[0199] Infrared spectrum: IR (thin film) 3609, 2924, 2858, 1462, 1368, 1315, 1264, 1218, 1140, 1102, 1042, 1008cm -1 .

[0200] High resolution mass spectrometry: HRMS m / z(CI)calculated for C 21 H 41 BNaO3[M+Na] + :375.3041,found:375.3045.

[0201] From the result, it can be seen that its theoretical mass is 375.3041, while the observed value of the peak found in the actual mass spectrum is 375.3045; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0202] Embodiment 18

[0203]

[0204] A method for preparing an alkenyl-substituted α-hydroxyboronic acid ester compound, as shown in the above reaction equation, this embodiment uses 76 mg of dec-5-yn-4-one and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, and follows the same steps as in Example 1, using 2.5 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, a colorless oily liquid of 89 mg, with a calculated yield of 63%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0205] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0206] 1 H NMR (400MHz, CDCl3) δ5.61 (dt, J=15.5, 6.7Hz, 1H), 5.48 (dt, J=15.5, 1.1Hz, 1H ),2.03–1.98(m,2H),1.69–1.61(m,2H),1.55–1.18(m,19H),0.91–0.83(m,6H).

[0207] 13 C NMR (100MHz, CDCl3) δ134.6,127.9,84.2,41.9,32.0,31.6,24.5,22.0,18.0,14.5,13.8.

[0208] Infrared spectrum: IR (thin film) 2952, 2924, 1454, 1417, 1375, 1323, 1255, 1144 cm -1 .

[0209] High resolution mass spectrometry: HRMS m / z(ESI)calculated for C 16 H 31 BNaO3[M+Na] + :305.2258,found:305.2261.

[0210] From the result, it can be seen that its theoretical mass is 305.2258, while the observed value of the peak found in the actual mass spectrum is 305.2261; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0211] Embodiment 19

[0212]

[0213] A method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, as shown in the above reaction equation, uses 83 mg of alkynone (2-methyldec-5-yn-4-one) and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, follows the same steps as in Example 1, uses 2.5 mol% of ruthenium catalyst, reacts for 6 hours, and obtains the corresponding reaction product, a colorless oily liquid of 79 mg, with a calculated yield of 53%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0214] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0215] 1 H NMR (400MHz, CDCl3) δ5.62(dt,J=15.5,6.7Hz,1H),5.49(d,J=15.5Hz,1H),2.02(dd,J=13.4,6.5Hz,2H),1.87–1.77(m ,1H),1.66(s,1H),1.59(dd,J=14.2,7.2Hz,1H),1.42(dd,J=14.2,6.0Hz,1H),1.34–1.20(m,16H),0.94–0.84(m,9H).

[0216] 13 C NMR (100MHz, CDCl3) δ135.3,127.4,84.2,48.0,32.0,31.6,25.2,24.6,24.5,24.1,23.6,22.0,13.8.

[0217] Infrared spectrum: IR (thin film) 2925, 2866, 1456, 1423, 1377, 1323, 1257, 1138, 1057cm -1 .

[0218] High resolution mass spectrometry: HRMS m / z(ESI)calculated for C 17 H 32 BO2[M–OH] + :279.2490,found:279.2491.

[0219] From the result, it can be seen that its theoretical mass is 279.2490, while the observed value of the peak found in the actual mass spectrum is 279.2491; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product implemented in this example.

[0220] Embodiment 20

[0221]

[0222] A method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, as shown in the above reaction equation, uses 119 mg of ethyl 6-oxododec-7-ynoate and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, follows the same steps as in Example 1, uses 2.5 mol% of ruthenium catalyst, reacts for 6 hours, and obtains the corresponding reaction product, a colorless oily liquid of 101 mg, with a calculated yield of 57%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0223] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0224] 1H NMR(400MHz, CDCl3) δ5.59(dt,J=15.5,6.7Hz,1H),5.45(dt,J=15.6,1.1Hz,1H),4.06(q,J=7.1Hz ,2H),2.29–2.22(m,2H),1.99(dd,J=13.0,6.7Hz,2H),1.73–1.17(m,26H),0.83(t,J=7.1Hz,3H).

[0225] 13 C NMR (100MHz, CDCl3) δ173.6,134.3,128.1,84.2,60.0,39.1,34.4,32.0,31.5,25.3,24.5(2C),24.2,21.9,14.1,13.8.

[0226] Infrared spectrum: IR (thin film) 2978, 2929, 2866, 1732, 1454, 1377, 1323, 1252, 1147, 1032cm -1 .

[0227] High resolution mass spectrometry: HRMS m / z(ESI)calculated for C 20 H 36 BO4[M–OH] + :351.2701,found:351.2711.

[0228] From the result, it can be seen that its theoretical mass is 351.2701, while the observed value of the peak found in the actual mass spectrum is 351.2711; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product implemented in this example.

[0229] Embodiment 21

[0230]

[0231] A preparation of an alkenyl substituted-α-hydroxyboric acid ester compound, as shown in the above reaction equation, using 120 mg of alkynone (4-methyl-1-(4-(trifluoromethyl)phenyl)pent-1-yn-3-one) and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, following the same steps as in Example 1, using 10 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, 103 mg of light green solid, with a calculated yield of 56%. The obtained reaction product was analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis was as follows:

[0232] Hydrogen spectrum, carbon spectrum and fluorine spectrum of nuclear magnetic resonance analysis:

[0233] 1 H NMR (400MHz, CDCl3) δ7.53(d,J=8.3Hz,2H),7.46(d,J=8.2Hz,2H),6.70(d,J=16.0Hz,1H),6.40( d,J=16.0Hz,1H),2.07–1.94(m,2H),1.26(s,12H),1.04(d,J=6.8Hz,3H),0.89(d,J=6.9Hz,3H).

[0234] 13 C NMR (100MHz, CDCl3) δ 141.1, 137.0, 128.5 (q, J = 32.1Hz), 126.3, 125.9, 125.3 (q, J = 3.7Hz), 122.9, 84.7, 72.5, 35.3, 24.6, 24.5, 28.7, 15.8.

[0235] 19 F NMR (100MHz, CDCl3) δ–62.4.

[0236] Infrared spectrum: IR (thin film) 2977, 1615, 1373, 1321, 1263, 1163, 1121, 1067, 1016cm -1 .

[0237] High resolution mass spectrometry: HRMS m / z(ESI)calculated for C 19 H 26 BF3NaO3[M+Na] + :393.1819,found:393.1826.

[0238] From the result, it can be seen that its theoretical mass is 393.1819, while the observed value of the peak found in the actual mass spectrum is 393.1826; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0239] Embodiment 22

[0240]

[0241] Preparation of an alkenyl-substituted α-hydroxyboric acid ester compound, as shown in the above reaction equation, this embodiment uses 125 mg of alkynone (1-(4-bromophenyl)-4-methylpent-1-yn-3-one) and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, and follows the same steps as in Example 21, using 10 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, 97 mg of light yellow solid, with a calculated yield of 51%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0242] Hydrogen spectrum and carbon spectrum of nuclear magnetic resonance analysis:

[0243] 1 H NMR (400MHz, CDCl3) δ7.39(d,J=8.5Hz,2H),7.23(d,J=8.5Hz,2H),6.60(d,J=16.0Hz,1H),6.28(d,J=1 6.0Hz,1H),2.02–1.95(m,1H),1.91(s,1H),1.25(s,12H),1.03(d,J=6.8Hz,3H),0.88(d,J=6.9Hz,3H).

[0244] 13 C NMR (100MHz, CDCl3) δ136.5,135.0,141.4,127.7,126.0,120.4,84.6,35.2,24.6(2C),18.8,15.8.

[0245] Infrared spectrum: IR (thin film) 2958, 2920, 1429, 1375, 1323, 1257, 1107, 1059cm -1 .

[0246] High resolution mass spectrometry: HRMS m / z(ESI)calculated for C 18 H 25 BBrO2[M–OH] + :363.1125,found:363.1123.

[0247] From the result, it can be seen that its theoretical mass is 363.1125, while the observed value of the peak found in the actual mass spectrum is 363.1123; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0248] Embodiment 23

[0249]

[0250] Preparation of an alkenyl substituted-α-hydroxyboric acid ester compound, as shown in the above reaction equation, this embodiment uses 95 mg of alkynone (1-(3-fluorophenyl)-4-methylpent-1-yn-3-one) and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, and follows the same steps as in Example 21, using 10 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, 65 mg of white solid, with a calculated yield of 41%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0251] Hydrogen spectrum, carbon spectrum and fluorine spectrum of nuclear magnetic resonance analysis:

[0252] 1 H NMR (400MHz, CDCl3) δ7.27–7.21(m,1H),7.13(d,J=7.8Hz,1H),7.09–7.06(m,1H),6.88(td,J=8.3,1.8Hz,1H),6.63(d,J=15. 9Hz,1H),6.30(d,J=15.9Hz,1H),2.05–1.95(m,1H),1.89(s,1H),1.26(s,12H),1.03(d,J=6.8Hz,3H),0.89(d,J=6.9Hz,3H).

[0253] 13 C NMR (100MHz, CDCl3) δ163.1 (d, J = 243.1Hz), 140.0 (d, J = 7.8Hz), 135.6, 129.8 (d, J = 8.5Hz), 126.1 (d, J = 2 .5Hz), 122.2 (d, J = 2.4Hz), 113.5 (d, J = 21.2Hz), 112.5 (d, J = 21.6Hz), 84.6, 35.3, 24.6, 24.5, 18.8, 15.8.

[0254] 19 F NMR (100MHz, CDCl3) δ–113.9.

[0255] Infrared spectrum: IR (thin film) 2976, 1610, 1582, 1445, 1372, 1266, 1136cm -1 .

[0256] High resolution mass spectrometry: HRMS m / z(ESI)calculated for C 18 H 26BFNaO3[M+Na] + :343.1851,found:343.1853.

[0257] From the result, it can be seen that its theoretical mass is 343.1851, while the observed value of the peak found in the actual mass spectrum is 343.1853; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0258] Embodiment 24

[0259]

[0260] Preparation of an alkenyl substituted-α-hydroxyboric acid ester compound, as shown in the above reaction equation, this embodiment uses 103 mg of alkynone (1-(3-chlorophenyl)-4-methylpent-1-yn-3-one) and 141 mg of pinacol borane corresponding to the above equation as reaction raw materials, and follows the same steps as in Example 21, using 10 mol% of ruthenium catalyst, reacting for 6 hours, and obtaining the corresponding reaction product, a light green oily liquid of 88 mg, with a calculated yield of 53%. The obtained reaction product is analyzed by nuclear magnetic resonance, infrared and high-resolution mass spectrometry, and the test analysis is as follows:

[0261] Hydrogen spectrum, carbon spectrum and fluorine spectrum of nuclear magnetic resonance analysis:

[0262] 1 H NMR (400MHz, CDCl3) δ7.36–7.35(m,1H),7.22–7.18(m,2H),7.16–7.13(m,1H),6.61(d,J=15.9Hz,1H),6.30(d,J=15.9Hz, 1H), 2.00 (dq, J=13.7, 6.9Hz, 1H), 1.93 (d, J=10.4Hz, 1H), 1.25 (s, 12H), 1.03 (d, J=6.8Hz, 3H), 0.88 (d, J=6.9Hz, 3H).

[0263] 13 C NMR (100MHz, CDCl3) δ139.5,135.7,134.3,129.6,126.7,125.9(2C),124.6,84.6,35.3,24.6,18.8,15.8.

[0264] Infrared spectrum: IR (thin film) 2976, 1565, 1473, 1372, 1329, 1201, 1138, 1054cm -1 .

[0265] High resolution mass spectrometry: HRMS m / z(ESI)calculated for C 18 H 26 BClNaO3[M+Na] + :359.1556,found:359.1562.

[0266] From the result, it can be seen that its theoretical mass is 359.1556, while the observed value of the peak found in the actual mass spectrum is 359.1562; combined with nuclear magnetic resonance and infrared element analysis, it can be determined that the structure of the product is the product of this example.

[0267] Embodiment 25

[0268]

[0269] A method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, using R 1 isopropyl, R 2 α,β-unsaturated alkynone of n-octyl alkynone (2-methyltridec-4-yn-3-one) and pinacol borane are used as reaction raw materials, and [CpRu(MeCN)3]PF6 catalyst is used for reaction. The specific implementation process includes: under nitrogen protection, 20.8mg alkynone (0.10mmol), 28.2mg pinacol borane and 0.5mL dichloroethane solvent are added to a 4mL dry bottle, and then 1.1mg [CpRu(MeCN)3]PF6 (2.5mol%) is added. The reaction is carried out at room temperature for 6 hours, and the reaction equation is as above. After the reaction is completed, 15mg triethylamine is added to quench the reaction, and then the reaction solution is filtered with short silica gel, eluted with ether, concentrated and chromatographed with silica gel column to obtain 23.0mg of colorless oily liquid product, and the calculated yield is 68%. The obtained reaction product is analyzed by nuclear magnetic resonance, and the test analysis shows that the obtained product is consistent with the product obtained in Example 1.

[0270] Embodiment 26

[0271]

[0272] A method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, using R 1 isopropyl, R 2The alkynone (2-methyltridec-4-yn-3-one) of n-octyl and pinacol borane are used as reaction raw materials, and [CpRu(MeCN)3]PF6 catalyst is used for reaction. The specific implementation process includes: under nitrogen protection, 20.8mg alkynone (0.10mmol), 28.2mg pinacol borane and 0.5mL dichloroethane solvent are added to a 4mL dry bottle, and then 2.7mg [Cp*RuCl]4 (2.5mol%) is added. The reaction is carried out at room temperature for 6 hours, and the reaction equation is as above. After the reaction is completed, 15mg triethylamine is added to quench the reaction, and then the reaction solution is filtered through a short silica gel, eluted with ether, and concentrated. After that, 16.9mg of colorless oily liquid product is obtained by silica gel column chromatography, and the calculated yield is 50%. The obtained reaction product is analyzed by nuclear magnetic resonance, and the test analysis shows that the obtained product is consistent with the product obtained in Example 1.

[0273] Embodiment 27

[0274]

[0275] A method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, using R 1 isopropyl, R 2 The octyl alkynone (2-methyltridec-4-yn-3-one) and pinacol borane are used as reaction raw materials, and [CpRu(MeCN)3]PF6 catalyst is used for reaction. The specific implementation process includes: under nitrogen protection, 20.8 mg of alkynone (0.10 mmol), 28.2 mg of pinacol borane and 0.5 mL of dichloroethane solvent are added to a 4 mL dry bottle, and then 0.8 mg of [Cp*RuCl2] n (2.5mol%). The reaction was carried out at room temperature for 6 hours. The reaction equation is as above. After the reaction was completed, 15mg of triethylamine was added to quench the reaction, and then the reaction solution was filtered through a short section of silica gel, washed with ether, concentrated, and chromatographed on a silica gel column to obtain 16.6mg of a colorless oily liquid product, with a calculated yield of 49%. The obtained reaction product was analyzed by nuclear magnetic resonance, and the test analysis showed that the obtained product was consistent with the product obtained in Example 1.

[0276] It can be seen from the above Examples 1 to 27 of the present application that by adopting the preparation method of the alkenyl-substituted-α-hydroxyboric acid ester compound of the present example, combined with the use of a ruthenium catalyst and borane, it is possible to realize two consecutive hydroboration reactions of an α, β-unsaturated alkynyl ketone compound, efficiently and selectively synthesize the alkenyl-substituted-α-hydroxyboric acid ester compound, and determine the correctness of the structure through a variety of characterization detection methods.

[0277] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A method for preparing an alkenyl-substituted α-hydroxyboric acid ester compound, characterized in that: The following steps are involved: The α,β-unsaturated alkynone compound of formula I and the pinacol borane of formula II are subjected to a hydroboration reaction under a catalyst condition to obtain an alkenyl-substituted-α-hydroxyboric acid ester compound of formula III; Among them, R 1 Selected from C1-C 20 Alkyl, C1-C 20 Heteroalkyl, C3-C 20 Cycloalkyl, C3-C 20 Heterocycloalkyl, C1-C 20 Alkyloxycarbonyl (C1-C 20 ) alkyl, C1-C 20 Alkyloxycarbonyl (C1-C 20 ) heteroalkyl, C1-C 20 Alkyloxycarbonyl (C3-C 20 ) cycloalkyl, C1-C 20 Alkyloxycarbonyl (C3-C 20 ) any one of heterocycloalkyl; R 2 Selected from C1-C 20 Alkyl, C1-C 20 Heteroalkyl, C3-C 20 Cycloalkyl, C3-C 20 Heterocycloalkyl, C1-C 20 Alkyloxycarbonyl (C1-C 20 ) alkyl, C1-C 20 Alkyloxycarbonyl (C1-C 20 ) heteroalkyl, C1-C 20 Alkyloxycarbonyl (C3-C 20 ) cycloalkyl, C1-C 20 Alkyloxycarbonyl (C3-C 20 ) heterocycloalkyl, C6-C 14 Aromatic, C4-C 14 Heteroaromatic, substituted (C6-C 14 ) aromatic group, C6-C 14 Aromatic (C1-C 20 ) alkyl, C6-C 14 Aromatic oxygen (C1-C 20 ) alkyl, C4-C 14 Sulfonyloxy (C1-C 20 ) alkyl, C1-C 10 Ester group (C1-C 20 ) alkyl, cyano (C1-C 20 ) alkyl, halogen (C1-C 20 ) alkyl, hydroxyl (C1-C 20 ) alkyl; the substituted (C6-C 14 ) The substituents in the aromatic group are selected from halogen, C1-C 10 Alkyl, halogenated C1-C 10 At least one of the alkyl groups; The catalyst is selected from a ruthenium metal catalyst, and the ruthenium metal catalyst is selected from [Cp*Ru(MeCN)3]PF6, [CpRu(MeCN)3]PF6, [Cp*RuCl]4 and [Cp*RuCl2] n At least one of; The hydroboration reaction is carried out in an organic solvent, and the organic solvent is selected from at least one of dichloroethane, dichloromethane, chloroform, ethyl acetate, and acetonitrile.

2. The preparation method according to claim 1, characterized in that R 1 Selected from C1-C 10 Alkyl, C1-C 10 Heteroalkyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C1-C 10 Alkyloxycarbonyl (C1-C 10 ) alkyl, C1-C 10 Alkyloxycarbonyl (C3-C 10 ) any one of the heterocycloalkyl groups.

3. The preparation method according to claim 1, characterized in that: R 2 Selected from C1-C 10 Alkyl, C1-C 10 Heteroalkyl, C3-C 10 Cycloalkyl, C3-C 10 Heterocycloalkyl, C6-C 14 Aromatic, substituted (C6-C 14 ) aromatic group, C6-C 14 Aromatic (C1-C 10 ) alkyl, C6-C 14 Aromatic oxygen (C1-C 10 ) alkyl, C4-C 14 Sulfonyloxy (C1-C 10 ) alkyl, C1-C 10 Ester group (C1-C 10 ) alkyl, cyano (C1-C 10 ) alkyl, halogen (C1-C 10 ) alkyl, hydroxyl (C1-C 10 ) alkyl.

4. The preparation method according to claim 1, characterized in that: When R 2 Selected from substituted (C6-C 14 ) is an aromatic group, the aromatic group is selected from phenyl, and the substituent is selected from halogen, C1-C 10 Alkyl, halogenated C1-C 10 At least one of the alkyl groups.

5. The preparation method according to claim 1, characterized in that: The added amount of the catalyst is 2.5% to 10% of the molar amount of the α,β-unsaturated alkynyl ketone compound.

6. The preparation method according to any one of claims 1 to 5, characterized in that: The temperature of the hydroboration reaction is 20-40°C.

7. The preparation method according to any one of claims 1 to 5, characterized in that: The hydroboration reaction is carried out in a protective atmosphere, and the gas of the protective atmosphere is selected from at least one of nitrogen, argon and helium.

Images