Silicon-boron reagent, preparation method thereof and application of silicon-boron reagent in alkyne addition

Abstract

The invention provides a silicon-boron reagent, a preparation method thereof and application of the silicon-boron reagent in alkyne addition. The invention develops a Si-B silicon-boron reagent TBSQ of which a silicon atom is connected with 8-quinolyl as a guiding group, and the Si-B silicon-boron reagent TBSQ is applied to an alkyne addition reaction catalyzed by palladium to realize a trans-silicon-boronation reaction of terminal alkyne catalyzed by palladium, so that various valuable trans-1-boryl-2-silicon-based olefins with various structures are provided, and the application of the Si-B silicon-boron reagent TBSQ to the alkyne addition reaction catalyzed by palladium is realized. The strategy exhibits specific E-selectivity over a wide range of substrates including large steric hindrance alkynes. The obtained trans-1-boryl-2-silicon-based olefin can be used as an important synthetic building block, a silicon group and a boron group on a trans-1-boryl-2-silicon-based olefin product are fully distinguished and are converted step by step, a series of molecules with medicinal correlation are successfully synthesized, and the application potential is high.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of synthesis of new substances, and particularly to a silicon-boron reagent, a preparation method thereof and application thereof in alkyne addition. BACKGROUND

[0002] The silicon-boron reaction of alkyne, i.e. 1,2-addition of alkyne by a silicon-boron (Si-B) reagent, has become the most direct and atom-economical strategy for the simultaneous regio- and stereo-selective introduction of boron and silicon fragments on carbon-carbon unsaturated triple bonds. The resulting 1-boron-2-silene can be used as a versatile and multifunctional synthon in organic synthesis due to the orthogonal reactivity of silicon and boron functional groups, and can further realize site-selective transformation (such as Suzuki-Miyaura cross-coupling, Tamao-Fleming oxidation and halogenation reaction). In addition, the substitution of boron or silicon groups for functional groups has become a core strategy in the fields of material science and pharmaceutical chemistry, and is widely used to endow molecules with unique physiological and photoelectric properties. Since Ito and Suginome first realized the silicon-boron reaction of alkyne and Si-B compound in 1996, researches on expanding substrate diversity and regulating regioselectivity by developing different catalytic systems and Si-B reagents have continued to make progress. Although significant progress has been made in the study of alkyne silicon-boron reaction, most of the reported cases are carried out in cis-addition mode. This is because all transition metal-catalyzed Si-B addition of alkyne is initiated by the interaction of the transition metal empty orbital and the alkyne π orbital. So far, the method for directly synthesizing trans-1-boron-2-silene from alkyne and Si-B reagent is still very limited (reaction formula a). When studying the silicon-boron reaction of terminal alkyne and (chlorodimethylsilyl)pinacolborane, Suginome's research group realized the stereochemical inversion and obtained trans-1-boron-2-silene with an E:Z ratio of up to 93:7. However, this trans-silaboration strategy cannot be applied to highly hindered alkyne: for example, phenylacetylene and 3,3-dimethyl-1-butyne generate isomer mixtures with Z:E ratios of 62:38 and 90:10, respectively (reaction formula b). Thereafter, Sawamura, Santos and Suginome respectively realized transition metal-free or copper-catalyzed trans-silaboration, but the substrate range thereof is limited to internal alkyne esters, propargyl amides and aryl alkynes (reaction formula c).

[0003]

[0004] Therefore, there is still an urgent need to develop a trans-selective silaboration reaction with excellent compatibility and stereoselectivity for highly hindered terminal alkyne. SUMMARY

[0005] In view of the fact that the existing methods mainly present cis-selectivity and trans-selectivity silicon-boron reaction is still not perfect, especially for the problem of highly hindered terminal alkyne, the present application provides a silicon-boron reagent and a preparation method and application thereof. The present application develops a Si-B silicon-boron reagent TBSQ in which 8-quinolinyl is connected to a silicon atom as a guiding group, and applies it to a palladium-catalyzed alkyne addition reaction, realizes the palladium-catalyzed trans-silicon-boron reaction of terminal alkyne, and thus provides a plurality of valuable and structurally diverse trans-1-boryl-2-silyl alkenes. This conversion reaction has excellent functional group tolerance, has been applied to a plurality of substrate skeletons with terminal alkyne groups, and has specific E-form selectivity, wherein the alkyne group is also highly sterically hindered. By fully distinguishing and stepwise converting the silicon group and the boron group on the trans-1-boryl-2-silyl alkene product, a series of molecules with medicinal relevance are successfully synthesized, which fully demonstrates the strong application potential of trans-1-boryl-2-silyl alkene as a multifunctional building block in organic synthesis.

[0006] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions

[0007] The first aspect of the present application is to provide a silicon-boron reagent having a structure as shown in formula A:

[0008]

[0009] The second aspect of the present application is to provide a preparation method of a silicon-boron reagent, comprising the following steps:

[0010] Step (I): under a protective atmosphere, 8-bromoquinoline, n-butyllithium and Me2HSiCl are used as raw materials to react in an organic solvent to generate a compound as shown in formula B;

[0011] wherein the structural formula of formula B is

[0012] Step (II): under a protective atmosphere, the compound as shown in formula B and B2Pin2 are used as raw materials to react in an organic solvent under the action of a platinum catalyst to generate the silicon-boron reagent as shown in formula A.

[0013] As a preferred embodiment,

[0014] In step (I),

[0015] The molar ratio of 8-bromoquinoline, n-butyllithium and Me2HSiCl is 1:(0.5-2.0):(0.5-2.0); and / or,

[0016] The concentration of 8-bromoquinoline in the solvent is (0.1-2) mol / L; and / or,

[0017] The reaction temperature is from -78°C to room temperature; and / or,

[0018] The reaction time is 1 to 48 hours; and / or,

[0019] The organic solvent is at least one selected from tetrahydrofuran, 2-methyltetrahydrofuran, toluene, anhydrous diethyl ether, 1,2-dichloroethane, n-hexane, cyclohexane, n-heptane, n-octane, and dioxane; and / or,

[0020] In step (two),

[0021] The platinum catalyst is at least one selected from tetratetraphenylphosphine platinum, dichlorobis(triethylphosphine)platinum, dichloro(vinyl)dichloride platinum, (1,5-cyclooctadiene)dibromide platinum, 2,2'-bipyridinedichloride platinum, bis(acetylacetone)platinum, platinum dichloride, bis(acetonitrile)dichloride platinum, tris(dibenzylacetone)platinum, dichlorobis(triphenylphosphine)platinum, alkenylbis(triphenylphosphine)platinum, and [1,1'-bis(diphenylphosphine)ferrocene]dichloride platinum; and / or,

[0022] The molar ratio of formula B, platinum catalyst, and B2Pin2 is 1:(0.01~0.2):(1.0~5.0); and / or,

[0023] The concentration of formula B in the solvent is 0.1–1.0 mol / L; and / or,

[0024] The reaction temperature is 50–150°C; and / or,

[0025] The reaction time is 12–48 hours; and / or,

[0026] The organic solvent is at least one selected from cyclohexane, tetrahydrofuran, 2-methyltetrahydrofuran, toluene, anhydrous diethyl ether, 1,2-dichloroethane, n-hexane, n-heptane, n-octane, dioxane, alcohol, dichloromethane, and carbon tetrachloride.

[0027] A third aspect of the present invention is to provide a method for preparing trans-1-boron-2-silylene using the borosilicate reagent described in the first aspect of the present invention, comprising the following steps:

[0028] A borosilicate reagent is reacted with an alkyne in an organic solvent under the action of a catalyst to obtain the trans-1-boron-2-silylene compound shown in formula C.

[0029] The silicon-boron reagent is the silicon-boron reagent described in the first aspect of this invention;

[0030] The structural formula of alkynes is Where R is heteroaryl, naphthyl, R1is aryl, C1-C10 alkyl, C1-C10 alkoxy, C1-C10 ester, cyano, C1-C10 haloalkyl, C1-C10 aldehyde, nitro, pinacol boronate (BPin group), trimethylsilyl (TMS), C1-C10 alkynyl, n is an integer from 1 to 3;

[0031] The structure of the compound of formula C is wherein 8-Qu represents 8-quinolinyl of the compound of formula A, i.e. R corresponds to R in the alkyne compound.

[0032] As a preferred embodiment,

[0033] In the alkyne, R is R1is phenyl, C1-C5 alkyl (preferably C1-C3 alkyl), C1-C5 alkoxy (preferably C1-C3 alkoxy), C1-C5 ester (preferably C1-C3 ester), cyano, C1-C5 haloalkyl (preferably C1-C3 haloalkyl), C1-C5 aldehyde (preferably C1-C3 aldehyde), nitro, pinacol boronate (BPin group), trimethylsilyl (TMS), C1-C5 alkynyl (preferably C1-C3 alkynyl), n is an integer from 1 to 2; halogen is F, Br, Cl;

[0034] When R is heteroaryl, the heteroaryl is

[0035] The alkyne is selected from at least one of the following compounds:

[0036]

[0037] The catalyst is at least one of Pd(OAc)2, Pd(acac)2, Pd(PPh3)4, Pd(dba)2, Pd2(dba)3, Pd(dppf)Cl2, Pd(cod)Cl2, Pd(MeCN)2Cl2, NiCl2 DME, Ni(cod)2, Ni(OTf)2; and / or,

[0038] The organic solvent is at least one of cyclohexane, n-hexane, n-heptane, dichloromethane, tetrahydrofuran, methyl tert-butyl ether, methylcyclopentyl ether, acetonitrile, N,N-dimethylformamide, toluene, chlorobenzene, chloroform, 1,2-dichloroethane; and / or,

[0039] The molar ratio of the silicon-boron reagent, the olefin, the catalyst is 1:(0.5-5):(0.01-0.5); and / or,

[0040] The concentration of the silicon-boron reagent in the organic solvent is (0.05-1.0) mol / L; and / or,

[0041] The addition reaction temperature is 50-120℃; and / or,

[0042] The addition reaction time is 12-48 hours.

[0043] The fourth aspect of the present application is to provide a trans-1-boron-2-silene having a structural formula as shown in formula C:

[0044] The structure of the compound of formula C is In which, 8-Qu represents 8-quinolinyl of the compound of formula A, that is R corresponds to R in the alkyne compound of the third aspect of the present application;

[0045] Preferably, the formula C is selected from at least one of the following compounds:

[0046]

[0047]

[0048] The 1,2-silaboronation of alkyne is an important strategy to realize the regio- and stereo-selective synthesis of multifunctional 1-boron-2-silene. As a universal synthon, such compounds can realize diversified downstream conversion through the orthogonal reactivity of boron and silicon.

[0049] The fifth aspect of the present application is to provide an application of the trans-1-boron-2-silene of the fourth aspect of the present application as a synthetic building block in organic synthesis, preferably,

[0050] The application of compound C-1 in the structure of formula C as a synthetic building block in organic synthesis; the structural formula of compound C-1 is:

[0051]

[0052] Preferably,

[0053] The application 1 is that under the protective atmosphere, the compound C-1, the compound 2, the ligand, the additive are reacted in the solvent under the action of the palladium catalyst to obtain the compound shown in compound 3;

[0054] In which, the compound 2 is The compound 3 is

[0055] Preferably, in the application 1,

[0056] The palladium catalyst is at least one selected from Pd(acac)2, Pd(PPh3)4, Pd(dba)2, Pd2(dba)3, and Pd(OAc)2; and / or,

[0057] The ligand is P( t Bu)2Me、PMe3、P( t Bu)3、P( t At least one of Bu)Me2; and / or,

[0058] The additive is at least one selected from NaOH, KOH, LiOH, NaCO3, and K2CO3; and / or,

[0059] The molar ratio of compound C-1, compound 2, palladium catalyst, ligand, and additive is 1:(0.5–2.0):(0.01–0.5):(0.02–1.0):(1.0–5.0); and / or,

[0060] The concentration of compound C-1 in the solvent is (0.05–1.0) mol / L; and / or,

[0061] The reaction temperature is from room temperature to 100°C; and / or the reaction time is from 12 to 48 hours.

[0062] or,

[0063] Application 3 is: compound C-1 and copper acetate react in a solvent to obtain the compound shown in formula 7;

[0064] Equation 7 is

[0065] Preferably, in application 3,

[0066] The molar ratio of compound C-1 to copper acetate is 1:(0.2–2.0); and / or,

[0067] The solvent is at least one selected from anhydrous ethanol, N,N-dimethylformamide, toluene, anhydrous methanol, N,N-dimethylacetamide, and dichloromethane; and / or,

[0068] The concentration of compound C-1 in the solvent is (0.05–0.2) mol / L; and / or,

[0069] The reaction temperature is from room temperature to 100°C; and / or,

[0070] The reaction time is 2 to 12 hours;

[0071] or,

[0072] The application 4 is: under a protective atmosphere, the compound C-1, copper bromide, are reacted in a solvent to obtain a compound shown in formula 8;

[0073] The formula 8 is

[0074] Preferably, in the application 4,

[0075] The molar ratio of the compound C-1, copper bromide is 1: (1.0-5.0); and / or,

[0076] The solvent is at least one of anhydrous methanol, anhydrous ethanol, water, tetrahydrofuran, acetonitrile, isopropanol; and / or,

[0077] The concentration of the compound C-1 in the solvent is 0.01-0.5 mol / L; and / or,

[0078] The reaction temperature is room temperature to 120 DEG C; and / or,

[0079] The reaction time is 2-12 hours;

[0080] Or,

[0081] The application 5 is: under a protective atmosphere, the compound C-1, sodium azide, are reacted in a solvent under the action of a copper catalyst to obtain a compound shown in formula 9;

[0082] The formula 9 is

[0083] Preferably, in the application 5,

[0084] The copper catalyst is at least one of copper sulfate, copper acetate, cuprous iodide, cuprous bromide; and / or,

[0085] The solvent is at least one of anhydrous methanol, anhydrous ethanol, isopropanol, toluene, tetrahydrofuran, anhydrous diethyl ether; and / or,

[0086] The molar ratio of the compound C-1, sodium azide, copper catalyst is 1: (0.5-2.0): (0.1-1.0); and / or,

[0087] The concentration of the compound C-1 in the solvent is 0.01-1.0 mol / L; and / or,

[0088] The reaction temperature is room temperature to 60 DEG C; and / or,

[0089] The reaction time is 2-12 hours;

[0090] Or,

[0091] The application 6 is: under a protective atmosphere, the compound C-1, the compound 10, under the action of a rhodium catalyst, in a solvent, to obtain a compound shown in the compound 11;

[0092] The compound 10 is The compound 11 is

[0093] Preferably, in the application 6,

[0094] The rhodium catalyst is at least one of chloro(1,5-cyclooctadiene)rhodium dimer, hydroxyl(1,5-cyclooctadiene)rhodium dimer, acetylacetone bis(ethylene)rhodium, (1,5-cyclooctadiene)acetylacetone rhodium, and chloro(triphenylphosphine)rhodium; and / or,

[0095] The solvent is at least one of anhydrous methanol, anhydrous ethanol, water, tetrahydrofuran, toluene, and dichloromethane; and / or,

[0096] The molar ratio of the compound C-1, the compound 10, and the rhodium catalyst is 1:(0.5-2.0):(0.01-0.2); and / or,

[0097] The concentration of the compound C-1 in the solvent is 0.01-0.5 mol / L; and / or,

[0098] The reaction temperature is 50-130°C; and / or,

[0099] The reaction time is 6-24 hours.

[0100] As a preferred embodiment, the compound C-1 in the structure of formula C is used as a synthetic building block in organic synthesis; the structural formula of the compound C-1 is

[0101]

[0102] Preferably,

[0103] The application 2 is: step A: under a protective atmosphere, the compound C-1, the compound 4, and an additive are reacted in a solvent under the action of a palladium catalyst to obtain a compound shown in the compound 5 or the compound 6;

[0104] The compound 4 is The compound 5 is The compound 6 is

[0105] Preferably, in step A of the application 2,

[0106] the palladium catalyst is at least one selected from the group consisting of bis-tri-tert-butylphosphine palladium, tetra-triphenylphosphine palladium, palladium acetate, palladium triflate, tris(dibenzylideneacetone)dipalladium, palladium acetylacetone, DPPF palladium dichloride; and / or,

[0107] the additive is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, disodium hydrogen phosphate; and / or,

[0108] the solvent is at least one selected from the group consisting of tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane; and / or,

[0109] the molar ratio of the compound C-1, the compound 4, the palladium catalyst, the additive is 1:(1.0-2.0):(0.05-0.2):(1.0-3.0); and / or,

[0110] the concentration of the compound C-1 in the solvent is 0.05-0.2 mol / L; and / or,

[0111] the reaction temperature is room temperature to 100°C; and / or,

[0112] the reaction time is 12-48 hours;

[0113] Further preferably, the compound 5 is further used as a synthetic building block for further organic synthesis;

[0114] Step B-1: the compound 5, tetrabutylammonium fluoride, react in a solvent to obtain a compound shown in the compound 12;

[0115] wherein the compound 12 is

[0116] Preferably, in the step B-1 of the application 2,

[0117] the molar ratio of the compound 5, tetrabutylammonium fluoride is 1:(1.0-3.0); and / or,

[0118] the solvent is at least one selected from the group consisting of tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane; and / or,

[0119] the concentration of the compound 5 in the solvent is 0.05-0.2 mol / L; and / or,

[0120] the reaction temperature is room temperature to 60°C; and / or,

[0121] the reaction time is 2-24 hours;

[0122] or,

[0123] Step B-2: under a protective atmosphere, compound 5, 18-crown-6, potassium tert-butoxide, heavy water, are reacted in a solvent to obtain a compound represented by compound 13.

[0124] wherein compound 13 is

[0125] Preferably, in the step B-2 of application 2,

[0126] the molar ratio of compound 5, 18-crown-6, potassium tert-butoxide, heavy water is (1.0-3.0) : (1.0-3.0) : (1.0-3.0) : (2.0-10.0); and / or,

[0127] the solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane; and / or,

[0128] the concentration of compound 5 in the solvent is 0.05-0.2 mol / L; and / or,

[0129] the reaction temperature is room temperature to 100°C; and / or,

[0130] the reaction time is 2-24 hours.

[0131] or,

[0132] Step B-3: under a protective atmosphere, compound 5, meta-chloroperoxybenzoic acid, sodium bicarbonate, are reacted in a solvent to obtain a compound represented by compound 14.

[0133] wherein compound 14 is

[0134] Preferably, in the step B-3 of application 2,

[0135] the molar ratio of compound 5, meta-chloroperoxybenzoic acid, sodium bicarbonate is 1 : (1.0-3.0) : (1.0-3.0); and / or,

[0136] the solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane; and / or,

[0137] the concentration of compound 5 in the solvent is 0.05-0.2 mol / L; and / or,

[0138] the reaction temperature is room temperature to 60°C; and / or,

[0139] the reaction time is 2-24 hours.

[0140] or,

[0141] Step B-4: the compound 5, the compound 15, a ligand, an additive 1, an additive 2 are reacted in a solvent under the action of a palladium catalyst in a protective atmosphere to obtain a compound shown as the compound 16;

[0142] The compound 15 is The compound 16 is

[0143] Preferably, in the step B-4 of the application 2,

[0144] The palladium catalyst is at least one of dichlorobis(triphenylphosphine)palladium, palladium tetraphenylphosphine, palladium di-t-butylphosphine; and / or,

[0145] The ligand is at least one of triphenylphosphine, tri-furfuryl phosphine, tri-thiophenyl phosphine, tricyclohexylphosphine; and / or,

[0146] The additive 1 is at least one of cuprous iodide, cuprous bromide, cuprous chloride; and / or,

[0147] The additive 2 is at least one of tetrabutylammonium fluoride, tetramethylammonium fluoride, potassium fluoride; and / or,

[0148] The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide; and / or,

[0149] The molar ratio of the compound 5, the compound 15, the palladium catalyst, the ligand, the additive 1, the additive 2 is 1:(1.0-3.0):(0.02-0.2):(0.04-0.4):(0.5-3.0):(0.5-3.0); and / or,

[0150] The concentration of the compound 5 in the solvent is 0.02-0.2 mol / L; and / or,

[0151] The reaction temperature is 60-150°C; and / or,

[0152] The reaction time is 12-48 hours.

[0153] As a preferred embodiment,

[0154] The application 7 of the compound C-17 in the structure of formula C as a synthetic building block in organic synthesis comprises the following steps:

[0155] Step (1-1): the compound C-17, the compound 18, an additive are reacted in a solvent under the action of a rhodium catalyst in a protective atmosphere to obtain a compound shown as the compound 19;

[0156] Step (1-2): under the action of a palladium catalyst, compound 19, compound 20, a ligand, additive 1, additive 2 are reacted in a solvent to obtain a compound represented by compound 21;

[0157] Compound C-17 is Compound 18 is Compound 19 is Compound 20 is Compound 21 is

[0158] Preferably, in step (1-1) of application 7,

[0159] The rhodium catalyst is at least one of chloro(cyclooctadiene)rhodium dimer, dimeric hydroxo(1,5-cyclooctadiene)rhodium, acetylacetonato bis(ethylene)rhodium, (1,5-cyclooctadiene)acetylacetonato rhodium, chloro(triphenylphosphine)rhodium; and / or,

[0160] The additive is at least one of sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate; and / or,

[0161] The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, toluene, dioxane, methyl tert-butyl ether; and / or,

[0162] The molar ratio of the compound C-17, compound 18, rhodium catalyst, additive is (1.0-2.0):1:(0.01-0.1):(1.0-2.0); and / or,

[0163] The concentration of the compound C-17 in the solvent is 0.02-0.5 mol / L; and / or,

[0164] The reaction temperature is room temperature to 120°C; and / or,

[0165] The reaction time is 2-12 hours;

[0166] In step (1-2) of application 7,

[0167] The palladium catalyst is at least one of dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, palladium di-tert-butylphosphine; and / or,

[0168] The ligand is at least one of triphenylphosphine, tri-furfuryl phosphine, tri-thienyl phosphine, tricyclohexylphosphine; and / or,

[0169] The additive 1 is at least one of cuprous iodide, cuprous bromide, cuprous chloride; and / or,

[0170] The additive 2 is at least one of tetrabutylammonium fluoride, tetramethylammonium fluoride, potassium fluoride; and / or,

[0171] The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide; and / or,

[0172] The molar ratio of the compound 19, the compound 20, the palladium catalyst, the ligand, the additive 1, the additive 2 is 1:(1.0-3.0):(0.01-0.2):(0.02-0.4):(0.5-2.0):(0.5-2.0); and / or,

[0173] The concentration of the compound 19 in the solvent is (0.02-0.2) mol / L; and / or,

[0174] The reaction temperature is 100-180℃; and / or,

[0175] The reaction time is 6-24 hours;

[0176] Or,

[0177] The application 8 of the compound C-22 in the structure of formula C as a synthetic building block in organic synthesis comprises the following steps:

[0178] Step (2-1): under a protective atmosphere, the compound C-22, the compound 23, the additive are reacted in the solvent under the action of the palladium catalyst to obtain the compound represented by the compound 24;

[0179] Step (2-2): under a protective atmosphere, the compound 24, the compound 25, the ligand, the additive 1, the additive 2 are reacted in the solvent under the action of the palladium catalyst to obtain the compound represented by the compound 26;

[0180] The compound C-22 is The compound 23 is The compound 24 is The compound 25 is The compound 26 is

[0181] Preferably, in step (2-1) of the application 8,

[0182] The palladium catalyst is at least one of di-tri-tert-butylphosphine palladium, tetra-triphenylphosphine palladium, palladium acetate, palladium triflate, tris(dibenzylideneacetone)dipalladium, palladium acetylacetone, DPPF palladium dichloride; and / or,

[0183] The additive is at least one of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate; and / or,

[0184] The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, water, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide; and / or,

[0185] The molar ratio of the compound C-22, the compound 23, the palladium catalyst, the additive is 1: (0.5-2.0): (0.05-0.5): (1.0-3.0); and / or,

[0186] The concentration of the compound C-22 in the solvent is (0.05-0.2) mol / L; and / or,

[0187] The reaction temperature is room temperature to 120°C; and / or,

[0188] The reaction time is 12-48 hours;

[0189] In the step (2-2) of application 8,

[0190] The palladium catalyst is at least one of dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, palladium di-tert-butylphosphine; and / or,

[0191] The ligand is at least one of triphenylphosphine, tri (furfuryl) phosphine, tri (thiophenyl) phosphine, tricyclohexylphosphine; and / or,

[0192] The additive 1 is at least one of cuprous iodide, cuprous bromide, cuprous chloride; and / or,

[0193] The additive 2 is at least one of tetrabutylammonium fluoride, tetramethylammonium fluoride, potassium fluoride; and / or,

[0194] The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide; and / or,

[0195] The molar ratio of the compound 24, the compound 25, the palladium catalyst, the ligand, the additive 1, the additive 2 is 1: (0.5-3.0): (0.02-0.5): (0.04-1.0): (0.5-2.0): (0.5-2.0); and / or,

[0196] The concentration of the compound 24 in the solvent is (0.05-0.5) mol / L; and / or,

[0197] The reaction temperature is 100-180°C; and / or,

[0198] The reaction time is 6-24 hours.

[0199] As a preferred embodiment,

[0200] The application 9 of compound C-27 in the structure of formula C as a synthetic building block in organic synthesis comprises the following steps:

[0201] Step (3-1): under a protective atmosphere, compound C-27, compound 4, an additive are reacted in a solvent under the action of a palladium catalyst to obtain a compound represented by compound 28;

[0202] Step (3-2): under a protective atmosphere, compound 28, N-chlorosuccinimide, silver fluoride are reacted in a solvent to obtain a compound represented by compound 29;

[0203] Compound C-27 is Compound 4 is Compound 28 is Compound 29 is

[0204] Preferably, in step (3-1) of application 9,

[0205] The palladium catalyst is at least one of di-tri-tert-butylphosphine palladium, tetra-triphenylphosphine palladium, palladium acetate, palladium triflate, tris(dibenzylideneacetone) dipalladium, palladium acetylacetone, DPPF dichloropalladium; and / or,

[0206] The additive is at least one of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate; and / or,

[0207] The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, water, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide; and / or,

[0208] The molar ratio of compound C-27, compound 4, palladium catalyst, additive is 1:(1.5-3.0):(0.05-0.2):(2.0-4.0); and / or,

[0209] The concentration of compound C-27 in the solvent is (0.05-0.5) mol / L; and / or,

[0210] The reaction temperature is room temperature to 120°C; and / or,

[0211] The reaction time is 12-48 hours;

[0212] In step (3-2) of application 9,

[0213] The molar ratio of the compound 28, N-chlorosuccinimide, silver fluoride is 1:(1.0-3.0):(1.0-5.0); and / or,

[0214] The solvent is at least one of acetonitrile, tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide; and / or,

[0215] The concentration of the compound 28 in the solvent is (0.05-0.5) mol / L; and / or,

[0216] The reaction temperature is room temperature to 80°C; and / or,

[0217] The reaction time is 12-48 hours;

[0218] Or,

[0219] The application of the compound C-30 in the structure of formula C as a synthetic building block in organic synthesis 10 comprises the following steps:

[0220] Step (4-1): under a protective atmosphere, the compound 30, the compound 31, an additive are reacted in a solvent under the action of a palladium catalyst to obtain a compound represented by the compound 32;

[0221] Step (4-2): the compound 32, tetrabutylammonium fluoride are reacted in a solvent to obtain a compound represented by the compound 33;

[0222] The compound C-30 is The compound 31 is The compound 32 is The compound 33 is

[0223] In step (4-1),

[0224] The palladium catalyst is at least one of di-tri-tert-butylphosphine palladium, tetra-triphenylphosphine palladium, palladium acetate, palladium triflate, tris(dibenzylideneacetone)dipalladium, palladium acetylacetone, DPPF dichloropalladium; and / or,

[0225] The additive is at least one of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate; and / or,

[0226] The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, water, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide; and / or,

[0227] The molar ratio of the compound C-30, the compound 31, the palladium catalyst, the additive is 1:(1.5-3.0):(0.05-0.5):(1.0-4.0); and / or,

[0228] The concentration of the compound C-30 in the solvent is (0.05-0.5) mol / L; and / or,

[0229] The reaction temperature is room temperature to 120 DEG C; and / or,

[0230] The reaction time is 12-48 hours;

[0231] In step (4-2),

[0232] The molar ratio of the compound 32, tetrabutylammonium fluoride is 1:(1.0-5.0); and / or,

[0233] The concentration of the compound 32 in the solvent is (0.05-0.5) mol / L; and / or,

[0234] The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide; and / or,

[0235] The reaction temperature is room temperature to 60 DEG C; and / or,

[0236] The reaction time is 6-24 hours.

[0237] Beneficial effects:

[0238] The application provides a simple and practical preparation method of a novel silicon boron reagent, and solves the problem of low trans-selectivity in traditional strategies in alkyne addition reaction, and importantly, a drug molecule (intermediate) or material molecule can be synthesized through two-step functional group transformation.

[0239] (1), the application develops a silicon boron reagent TBSQ which introduces 8-quinolinyl as a guiding group on a silicon atom.

[0240] (2), the application first realizes trans-silaboration of terminal alkyne under the condition of palladium catalysis using TBSQ reagent, generates trans-1-boryl-2-silyl alkene with high E formula selectivity, and solves the problem that it is difficult to perform trans-silaboration on terminal alkyne with large steric hindrance in the previous method.

[0241] (3), the trans-1-boryl-2-silyl alkene generated by the application is a multifunctional building block in organic synthesis, through step-by-step transformation of the boryl and silyl groups, a variety of molecules and photochromic materials with medicinal relevance can be efficiently synthesized.

[0242] In summary, the present application discloses a palladium-catalyzed trans-silaboration of terminal alkynes using a silaborating reagent TBSQ bearing an 8-quinolyl directing group on the silicon atom. This strategy exhibits exclusive E-selectivity over a broad range of substrates including highly hindered alkynes. The resulting trans-1-boryl-2-silyl alkenes can serve as important synthetic building blocks for the selective applications of drug-related molecules. DETAILED DESCRIPTION

[0243] Preparation Example 1

[0244] The present application provides a silaborating reagent TBSQ, having a structure as shown in Formula A

[0245]

[0246] The preparation method of the silaborating reagent comprises the following steps:

[0247] Step one:

[0248]

[0249] In a protective atmosphere, 8-bromoquinoline, n-butyllithium, Me2HSiCl are used as raw materials to react in a solvent to generate a compound as shown in Formula B; the specific implementation method is as follows:

[0250] Under an argon atmosphere, 8-bromoquinoline (4.2 g, 20 mmol) is dissolved in 50 mL of anhydrous tetrahydrofuran, cooled to -78°C, and then n-butyllithium solution (2.5 mol / L, 24 mmol, 9.6 mL) is slowly added dropwise into the reaction bottle. After the dropwise addition is completed, the mixture is continuously stirred at -78°C for 30 minutes. Then dimethylchlorosilane (2.27 g, 24 mmol) is added, and stirred at -78°C for another 10 minutes, then naturally warmed to room temperature and reacted overnight. After the raw material is completely reacted, saturated ammonium chloride solution is added to quench the reaction, and extracted with diethyl ether (30 mL x 3). The organic phase is washed with salt water, dried with anhydrous sodium sulfate, filtered and concentrated by rotary evaporation, and then separated and purified by reduced pressure distillation to obtain colorless oily product dimethylquinolylsilane II (3.1 g, yield 83%);

[0251] 1H NMR (400 MHz, CDC13) δ 9.02 - 8.92 (m, 1H), 8.15 (dt, J = 8.3, 1.6 Hz, 1H), 7.99 (dt, J = 6.7, 1.5 Hz, 1H), 7.87 (dt, J = 8.2, 1.5 Hz, 1H), 7.56 (ddd, J = 8.1, 6.6, 1.3 Hz, 1H), 7.41 (ddd, J = 8.3, 4.2, 1.3 Hz, 1H), 4.87 (td, J = 3.7, 1.4 Hz, 1H), 0.59 (dd, J = 3.8, 1.3 Hz, 6H). 13 C NMR (101 MHz, CDC13) δ 152.68, 149.55, 139.32, 136.62, 136.26, 129.53, 127.75, 126.21, 120.95, -3.03. HRMS (ESI) calcd. For C 11 H 14 NSi[M+H] + : 188.0896. Found: 188.0887.

[0252] Step two,

[0253]

[0254] In a protective atmosphere, a compound shown in formula B, B2Pin2, is used as a raw material, platinum is used as a catalyst, and a reaction is carried out in a solvent to generate a compound shown in formula A; the specific implementation method is as follows:

[0255] Into a 100 mL thick-walled pressure-resistant reaction bottle, B2Pin2(10.2 g, 40 mmol, 2.5 eq), Pt(PPh3)4(398 mg, 0.32 mmol) and cyclohexane (32 mL, 0.5 M) were added, followed by adding a compound shown in formula B (3.0 g, 16 mmol). The mixture was reacted at 100°C for 48 hours. After the raw material was completely reacted, it was filtered through silica gel and washed with a mixed solvent of petroleum ether: ethyl acetate = 10:1, and the filtrate was concentrated under reduced pressure and purified by reverse phase column chromatography (C18(ODS) stationary phase, eluent: water / acetonitrile system) to obtain pure product TBSQ (4.2 g, yield 83%).

[0256] 1H NMR (400 MHz, CDC13) δ 8.84 (dt, J = 4.0, 2.0 Hz, 1H), 8.07 (dt, J = 8.4, 1.9 Hz, 1H), 7.96 - 7.85 (m, 1H), 7.76 (dt, J = 8.2, 1.7 Hz, 1H), 7.49 (td, J = 7.3, 2.2 Hz, 1H), 7.37 - 7.28 (m, 1H), 1.22 (d, J = 2.5 Hz, 12H), 0.45 (d, J = 2.4 Hz, 6H). 13 C NMR (101 MHz, CDC13) δ 152.45, 148.84, 141.36, 136.05, 135.92, 128.77, 127.65, 126.36, 120.70, 83.08, 25.02, -3.05. HRMS (EI) calcd. For C 17 H 24 BNO2Si[M] + : 313.1669. Found: 313.1659.

[0257] The present application provides the application of silicon boron reagent in alkyne addition reaction, realizing the regioselective and stereoselective synthesis of multifunctional 1-boron-2-silene: formula A (TBSQ), alkyne reacts under the action of catalyst in solvent to obtain the compound shown in formula C; the reaction process is as shown below, and the reaction formula is as follows:

[0258]

[0259] The following examples will help understand the present application, but are not limited to the content of the present application:

[0260] Example 1:

[0261] In a nitrogen glove box, after a dried 15 mL pressure tube was equipped with a polytetrafluoroethylene magnetic stirrer, Pd(OAc)2(4.5 mg, 0.02 mmol), dichloromethane (2 mL), TBSQ reagent of formula A (62.6 mg, 0.2 mmol) and phenylacetylene (0.4 mmol, 2.0 equivalents) were sequentially added. The reaction tube was removed from the glove box and placed in a heating block preheated to 80°C, and stirred vigorously under a nitrogen (N2) atmosphere for 24 hours. After the reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation under reduced pressure, and the residue was separated and purified by silica gel flash column chromatography to obtain the target product (E)-8-(dimethyl(1-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)silyl)quinoline, with a yield of 82%.

[0262] 1H NMR (400 MHz, CDC13) δ 8.85 (q, J = 1.6 Hz, 1H), 8.08 (dt, J = 8.3, 1.4 Hz, 1H), 7.92 (d, J = 6.8 Hz, 1H), 7.80 (d, J = 8.1 Hz, 1H), 7.48 (t, J = 7.4 Hz, 1H), 7.33 (dd, J = 8.2, 4.2 Hz, 1H), 7.13 (p, J = 6.8 Hz, 3H), 7.09 - 7.01 (m, 2H), 6.22 (s, 1H), 1.06 (s, 12H), 0.53 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 166.71, 152.72, 149.12, 145.60, 139.68, 137.16, 135.95, 129.41, 127.77, 127.62, 127.32, 126.06, 125.71, 120.77, 83.18, 24.71, -1.13. HRMS (ESI) calcd. For C 25 H 30 BNO2Si[M + H] + : 416.2217. Found: 416.2215.

[0263] Example 2:

[0264] The reaction procedure was the same as Example 1, except that 4-phenylphenylacetylene was used as the starting material. After purification, (E)-8-((l-([l,r-biphenyl]-4-yl)-2-(4,4,5,5-tetramethyl-l,3,2-dioxaborinan-2-yl)vinyl)dimethylsilanyl)quinoline was obtained in 91% yield.

[0265] 1 H NMR (400 MHz, CDC13) δ 8.86 (dd, J = 4.1, 1.8 Hz, 1H), 8.09 (dd, J = 8.3, 1.9 Hz, 1H), 7.95 (dd, J = 6.7, 1.5 Hz, 1H), 7.81 (dd, J = 8.1, 1.5 Hz, 1H), 7.57 (dd, J = 8.3, 1.3 Hz, 2H), 7.50 (dd, J = 8.1, 6.7 Hz, 1H), 7.45 - 7.39 (m, 4H), 7.36 - 7.29 (m, 2H), 7.17 - 7.11 (m, 2H), 6.26 (s, 1H), 1.08 (s, 12H), 0.57 (s, 6H). 13C NMR (101 MHz, CDC13) δ 166.36, 152.73, 149.14, 144.80, 141.56, 139.66, 138.48, 137.19, 135.97, 129.46, 128.79, 128.14, 127.80, 127.02, 126.96, 126.08, 126.05, 120.80, 83.26, 24.74, -1.07. HRMS (ESI) calcd. For C 31 H 34 BNO2Si [M + H] + : 492.2530. Found: 492.2533.

[0266] Example 3:

[0267] The reaction procedure was the same as Example 1, except that 4-tert- butylphenylacetylene was used as the starting material. After purification, (E)-8-((l-(4-(tert- butyl)phenyl)-2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)dimethylsilanyl) quinoline was obtained in 74% yield.

[0268] 1 H NMR (400 MHz, CDC13) δ 8.85 (dd, J = 3.9, 1.9 Hz, 1H), 8.08 (dd, J = 8.3, 1.8 Hz, 1H), 7.96 (d, J = 6.5 Hz, 1H), 7.80 (d, J = 8.1 Hz, 1H), 7.49 (t, J = 7.5 Hz, 1H), 7.32 (dd, J = 8.2, 4.1 Hz, 1H), 7.18 (d, J = 7.9 Hz, 2H), 7.02 (d, J = 7.9 Hz, 2H), 6.22 (s, 1H), 1.28 (s, 9H), 1.07 (s, 12H), 0.55 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 166.19, 152.76, 149.09, 148.56, 142.67, 139.84, 137.26, 135.94, 129.35, 127.77, 127.32, 126.05, 124.21, 120.72, 83.14, 34.43, 31.55, 24.72, -1.06. HRMS (ESI) calcd. For C 29 H 38 BNO2Si [M + H] + : 472.2843. Found: 472.2841.

[0269] Example 4:

[0270] The reaction procedure was same as Example 1 except that 4- methoxyphenylacetylene was used as starting material. After purification of the crude product, (E)-8-((l-(4-methoxyphenyl)-2- (4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)dimethylsilanyl)quinoline was obtained in 89% yield.

[0271] 1 H NMR (400 MHz, CDC13) δ 8.82 (dt, J = 4.0, 2.2 Hz, 1H), 8.04 (tt, J = 6.6, 1.9 Hz, 2H), 7.76 (dt, J = 8.1, 1.8 Hz, 1H), 7.54 - 7.45 (m, 1H), 7.29 (ddd, J = 8.2, 4.2, 2.1 Hz, 1H), 7.25 - 7.19 (m, 2H), 6.74 (dd, J = 8.6, 2.2 Hz, 2H), 6.20 (d, J = 2.1 Hz, 1H), 3.75 (s, 2H), 0.99 (s, 12H), 0.57 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 168.37, 157.89, 152.14, 148.71, 142.55, 141.76, 137.09, 135.86, 128.80, 128.10, 127.54, 125.90, 120.52, 112.83, 83.11, 55.27, 24.74, 0.80. HRMS (ESI) calcd. For C 26 H 32 BNO3Si[M + H] + : 446.2223. Found: 446.2321.

[0272] Example 5:

[0273] The reaction procedure was same as Example 1 except that 4- methoxyphenylacetylene was used as starting material. After purification of the crude product, (E)-8-((l-(4-methoxyphenyl)-2- (4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)dimethylsilanyl)quinoline was obtained in 89% yield.

[0274] 1H NMR (400 MHz, CDC13) δ 8.81 (dd, J = 4.3, 1.8 Hz, 1H), 8.03 (td, J = 7.7, 6.9, 1.7 Hz, 2H), 7.76 (dd, J = 8.2, 1.5 Hz, 1H), 7.48 (dd, J = 8.1, 6.7 Hz, 1H), 7.33 - 7.24 (m, 1H), 7.20 - 7.12 (m, 2H), 6.74 - 6.65 (m, 2H), 6.21 (s, 1H), 4.46 (hept, J = 6.1 Hz, 1H), 1.28 (d, J = 6.0 Hz, 7H), 1.00 (s, 12H), 0.58 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 168.45, 156.17, 152.17, 148.71, 142.39, 141.85, 137.07, 135.82, 128.77, 128.09, 127.54, 125.91, 120.50, 114.93, 83.11, 69.91, 24.76, 22.24, 0.83. HRMS (ESI) calcd. For C 28 H 37 BNO3Si[M + H] + : 474.2558. Found: 474.2558.

[0275] Example 6:

[0276] The reaction procedure was the same as Example 1 except that 4-fluorophenylacetylene was used as starting material. After purification, (E)-8-((l-(4-fluorophenyl)-2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)dimethylsilanyl)quinoline was obtained in 91% yield.

[0277] 1 H NMR (400 MHz, CDC13) δ 8.84 (dt, J = 2.9, 1.5 Hz, 1H), 8.08 (dt, J = 8.3, 1.5 Hz, 1H), 7.90 (dd, J = 6.8, 1.5 Hz, 1H), 7.80 (dd, J = 8.1, 1.4 Hz, 1H), 7.49 (dd, J = 8.2, 6.7 Hz, 1H), 7.42 - 7.29 (m, 1H), 7.00 (dd, J = 8.4, 5.6 Hz, 2H), 6.84 (td, J = 8.7, 7.6, 3.8 Hz, 2H), 6.24 (s, 1H), 1.08 (s, 12H), 0.53 (s, 6H). 13C NMR (101 MHz, CDC13) δ 166.18, 161.56 (d, J = 242.8 Hz), 152.61, 149.11, 141.43 (d, J = 3.2 Hz), 139.39, 137.02, 135.97, 129.51, 129.02 (d, J = 7.7 Hz), 127.75, 126.05, 120.81, 113.98 (d, J = 21.2 Hz), 83.20, 24.70, -1.23. 19 F NMR (376 MHz, CDC13) δ -118.38. HRMS (ESI) calcd for C 25 H 29 BFNO2Si [M + H] + : 434.2123. Found: 434.2124.

[0278] Example 7:

[0279] The reaction procedure was the same as Example 1, except that 4-bromo-phenylacetylene was used as the starting material. After purification, (E)-8-((l-(4-bromophenyl)-2- (4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)dimethylsilanyl)quinoline was obtained in 54% yield.

[0280] 1 H NMR (400 MHz, CDC13) δ 8.80 (dd, J = 4.2, 1.8 Hz, 1H), 8.06 (dd, J = 8.3, 1.8 Hz, 1H), 8.00 (dd, J = 6.7, 1.5 Hz, 1H), 7.78 (dd, J = 8.2, 1.5 Hz, 1H), 7.50 (dd, J = 8.1, 6.7 Hz, 1H), 7.32 - 7.27 (m, 3H), 7.17 - 7.10 (m, 2H), 6.15 (s, 1H), 1.01 (s, 12H), 0.55 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 167.90, 151.98, 148.95, 148.74, 141.25, 137.03, 135.94, 130.41, 129.01, 128.74, 127.56, 125.93, 120.63, 119.59, 83.31, 24.76, 0.52. HRMS (ESI) calcd for C 25 H 29 BBrNO2Si [M + H] + : 494.1322. Found: 494.1319.

[0281] Example 8:

[0282] The reaction procedure was the same as Example 1 except that methyl 4-ethynylbenzoate was used as the starting material. After purification, methyl (E)-4-(l-(dimethyl(quinolin-8-yl)silyl)-2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)benzoate was obtained in 87% yield.

[0283] 1 H NMR (400 MHz, CDC13) δ 8.82 (dd, J = 4.2, 1.8 Hz, 1H), 8.07 (dd, J = 8.3, 1.9 Hz, 1H), 7.97 - 7.73 (m, 4H), 7.47 (dd, J = 8.1, 6.7 Hz, 1H), 7.32 (dd, J = 8.2, 4.2 Hz, 1H), 7.14 - 7.01 (m, 2H), 6.26 (s, 1H), 3.87 (s, 3H), 1.04 (s, 12H), 0.52 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 167.58, 166.74, 152.52, 150.98, 149.12, 139.04, 136.96, 135.97, 129.59, 128.67, 127.73, 127.56, 127.29, 126.03, 120.84, 83.27, 51.97, 24.66, -1.31. HRMS (ESI) calcd. For C 27 H 32 BNO4Si [M+H] + : 474.2272. Found: 474.2272.

[0284] Example 9:

[0285] The reaction procedure was the same as Example 1 except that 4-ethynylbenzonitrile was used as the starting material and the reaction time was 48 h. After purification, (E)-4-(l-(dimethyl(quinolin-8-yl)silyl)-2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)benzonitrile was obtained in 60% yield.

[0286] 1H NMR (400 MHz, CDC13) δ 8.79 (dd, J = 4.2, 1.6 Hz, 1H), 8.09 (dd, J = 8.3, 1.8 Hz, 1H), 7.94 - 7.75 (m, 2H), 7.48 (dd, J = 8.1, 6.7 Hz, 1H), 7.40 (d, J = 7.9 Hz, 2H), 7.33 (dd, J = 8.2, 4.2 Hz, 1H), 7.06 (d, J = 7.9 Hz, 2H), 6.26 (s, 1H), 1.04 (s, 12H), 0.52 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 166.73, 152.41, 151.12, 149.12, 138.63, 136.89, 136.04, 131.01, 129.77, 128.24, 127.75, 126.08, 120.93, 119.77, 108.99, 83.36, 24.67, -1.40. HRMS (ESI) calcd. For C 26 H 29 BN2O2Si[M + H] + : 441.2170. Found: 441.2172.

[0287] Example 10:

[0288] The reaction procedure was the same as Example 1, except that 4- trifluoromethylphenylacetylene was used as the starting material. After purification, (E)-8-(dimethyl(2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-l-(4- (trifluoromethyl)phenyl)vinyl)silyl)quinoline was obtained in 87% yield.

[0289] 1 H NMR (400 MHz, CDC13) δ 8.82 (dd, J = 4.2, 1.8 Hz, 1H), 8.09 (dd, J = 8.2, 1.8 Hz, 1H), 7.89 (dd, J = 6.7, 1.5 Hz, 1H), 7.82 (dd, J = 8.1, 1.5 Hz, 1H), 7.49 (dd, J = 8.1, 6.7 Hz, 2H), 7.40 (d, J = 8.0 Hz, 1H), 7.33 (dd, J = 8.2, 4.2 Hz, 2H), 7.11 (d, J = 7.9 Hz, 1H), 6.28 (s, 0H), 1.04 (s, 12H), 0.54 (s, 6H). 13C NMR (101 MHz, CDC13) δ 166.48, 152.54, 149.64, 149.63, 149.14, 138.96, 136.97, 136.00, 129.66, 127.78, 127.77 (q, J = 32.3 Hz) 126.07, 124.75 (q, J = 272.7 Hz). 124.11 (q, J = 3.9 Hz), 120.88, 83.29, 24.64, -1.35. 19 FNMR (376 MHz, CDC13) δ -62.14. HRMS (ESI) calcd. For C 26 H 29 BF3NO2Si[M + H] + : 484.2091. Found: 484.2093.

[0290] Example 11:

[0291] The reaction procedure was the same as Example 1, except that 4-ethynylbenzaldehyde was used as the starting material. After purification, (E)-4-(l-(dimethyl(quinolin-8-yl)silyl)-2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)benzaldehyde was obtained in 67% yield.

[0292] 1 H NMR (400 MHz, CDC13) δ 9.92 (s, 1H), 8.81 (dd, J = 4.2, 1.8 Hz, 1H), 8.07 (dd, J = 8.3, 1.9 Hz, 1H), 7.87 (dd, J = 6.7, 1.5 Hz, 1H), 7.80 (dd, J = 8.2, 1.5 Hz, 1H), 7.70 - 7.62 (m, 2H), 7.48 (dd, J = 8.2, 6.7 Hz, 1H), 7.32 (dd, J = 8.3, 4.1 Hz, 1H), 7.16 (d, J = 8.1 Hz, 2H), 6.28 (s, 1H), 1.03 (s, 12H), 0.53 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 192.47, 166.87, 152.96, 152.45, 149.12, 138.83, 136.92, 136.00, 134.07, 129.68, 128.94, 128.16, 127.72, 126.05, 120.88, 83.30, 24.64, -1.33. HRMS (ESI) calcd. For C 26 H 32 BNO3Si[M + H]+ :444.2166.Found:444.2165.

[0293] Example 12:

[0294] The reaction procedure was the same as Example 1 except that 4-nitrophenylacetylene was used as the starting material. After purification, (E)-8-(dimethyl(1-(4-nitrophenyl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)silyl)quinoline was obtained in 69% yield.

[0295] 1 H NMR (400 MHz, CDC13) δ 8.86 - 8.75 (m, 1H), 8.09 (d, J = 8.1 Hz, 1H), 7.98 (dd, J = 8.7, 2.2 Hz, 2H), 7.89 - 7.79 (m, 2H), 7.54 - 7.45 (m, 1H), 7.34 (dd, J = 8.5, 4.1 Hz, 1H), 7.11 (dd, J = 8.7, 2.2 Hz, 2H), 1.03 (d, J = 2.1 Hz, 12H), 0.53 (d, J = 2.1 Hz, 6H). 13 CNMR (101 MHz, CDC13) δ 166.69, 153.42, 152.39, 149.14, 146.03, 138.51, 136.89, 136.08, 129.84, 128.25, 127.77, 126.11, 122.48, 120.97, 83.41, 24.68, -1.40. HRMS (ESI) calcd. For C 25 H 29 BN2O4Si[M + H] + :461.2068.Found:461.2071.

[0296] Example 13:

[0297] The reaction procedure was the same as Example 1 except that 4-ethynylphenylboronic acid pinacol ester was used as the starting material. After purification, (E)-8-(dimethyl(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)vinyl)silyl)quinoline was obtained in 63% yield.

[0298] 1H NMR (400 MHz, CDC13) δ 8.84 (dd, J = 4.2, 1.8 Hz, 1H), 8.08 (dd, J = 8.2, 1.9 Hz, 1H), 7.89 (dd, J = 6.7, 1.5 Hz, 1H), 7.79 (dd, J = 8.1, 1.5 Hz, 1H), 7.65 - 7.58 (m, 2H), 7.47 (dd, J = 8.1, 6.7 Hz, 1H), 7.33 (dd, J = 8.2, 4.1 Hz, 1H), 7.08 - 7.01 (m, 2H), 6.21 (s, 1H), 1.33 (s, 12H), 1.06 (s, 12H), 0.50 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 166.75, 152.66, 149.16, 148.69, 139.54, 137.14, 135.96, 133.95, 127.76, 127.03, 126.05, 120.78, 83.64, 83.23, 25.02, 24.70, -1.15. HRMS (ESI) calcd. For C 31 H 41 B2NO4Si[M + H] + : 542.3069. Found: 542.3080.

[0299] Example 14:

[0300] The reaction procedure was the same as Example 1, except that (4-ethynylphenyl)trimethylsilane was used as the starting material. After purification, (E)-8-(dimethyl(2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-l-(4-(trimethylsilyl)phenyl)vinyl)silyl)quinoline was obtained in 77% yield.

[0301] 1 H NMR (400 MHz, CDC13) δ 8.82 (dd, J = 4.1, 2.0 Hz, 1H), 8.06 - 7.98 (m, 2H), 7.81 - 7.73 (m, 1H), 7.48 (t, J = 7.5 Hz, 1H), 7.36 - 7.30 (m, 2H), 7.29 - 7.25 (m, 1H), 7.23 (d, J = 7.8 Hz, 2H), 6.21 (s, 1H), 0.98 (s, 12H), 0.56 (s, 6H), 0.22 (s, 9H). 13C NMR (101 MHz, CDC13) δ 168.88, 152.20, 150.32, 148.74, 141.77, 137.11, 137.04, 135.80, 132.46, 128.79, 127.57, 126.33, 125.92, 120.51, 83.15, 24.75, 0.79, -0.89. HRMS (ESI) calcd. For C 28 H 39 BNO2Si2[M + H] + : 488.2534. Found: 488.2533.

[0302] Example 15:

[0303] The reaction procedure was the same as Example 1, except that 3-methylphenylacetylene was used as the starting material. After purification, (E)-8-(dimethyl(2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-l-(m-tolyl)vinyl)silyl)quinoline was obtained in 84% yield.

[0304] 1 H NMR (400 MHz, CDC13) δ 8.86 (dd, J = 4.2, 1.8 Hz, 1H), 7.49 (dd, J = 8.1, 6.7 Hz, 1H), 7.33 (dd, J = 8.3, 4.2 Hz, 1H), 7.05 (t, J = 7.8 Hz, 1H), 6.96 - 6.91 (m, 1H), 6.90 - 6.85 (m, 2H), 6.22 (s, 1H), 2.24 (s, 3H), 1.08 (s, 12H), 0.54 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 166.56, 152.73, 149.10, 145.43, 139.78, 137.21, 136.54, 135.94, 129.37, 128.48, 127.77, 127.23, 126.49, 126.04, 124.70, 120.74, 83.15, 24.71, 21.54, -1.05. HRMS (ESI) calcd. For C 26 H 32 BNO2Si[M + H] + : 430.2374. Found: 430.2379.

[0305] Example 16:

[0306] The reaction procedure was the same as Example 1 except that 3- chlorophenylacetylene was used as starting material. After purification, (E)-8-((l-(3- chlorophenyl)-2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)dime- thylsilyl)quinoline was obtained in 91% yield.

[0307] 1 H NMR (400 MHz, CDC13) δ 8.85 (dd, J = 4.2, 1.8 Hz, 1H), 8.09 (dd, J = 8.3, 1.9 Hz, 1H), 7.90 (dd, J = 6.8, 1.5 Hz, 1H), 7.81 (dd, J = 8.2, 1.5 Hz, 1H), 7.49 (dd, J = 8.1, 6.7 Hz, 1H), 7.33 (dd, J = 8.2, 4.2 Hz, 1H), 7.16 - 7.05 (m, 1H), 6.86 - 6.74 (m, 3H), 6.24 (s, 1H), 1.08 (s, 12H), 0.54 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 165.93, 162.27 (d, J = 244.1 Hz), 152.59, 149.14, 147.98 (d, J = 7.5 Hz), 139.26, 137.02, 135.99, 129.56, 128.63 (d, J = 8.3 Hz), 127.77, 126.06, 123.29 (d, J = 2.8 Hz), 120.84, 114.62 (d, J = 21.2 Hz), 112.32 (d, J = 21.2 Hz), 83.26, 24.69, -1.23. 19 F NMR (376 MHz, CDC13) δ -115.34. HRMS (ESI) calcd. For C 25 H 29 BFNO2Si[M + H] + : 434.2123. Found: 434.2121.

[0308] Example 17:

[0309] The reaction procedure was the same as Example 1 except that 3- chlorophenylacetylene was used as starting material. After purification, (E)-8-((l-(3- chlorophenyl)-2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)dime- thylsilyl)quinoline was obtained in 91% yield.

[0310] 1H NMR (400 MHz, CDC13) δ 8.84 (dd, J = 4.2, 1.8 Hz, 1H), 8.09 (dd, J = 8.2, 1.8 Hz, 1H), 7.90 (dd, J = 6.8, 1.5 Hz, 1H), 7.81 (dd, J = 8.1, 1.5 Hz, 1H), 7.50 (dd, J = 8.1, 6.8 Hz, 1H), 7.34 (dd, J = 8.2, 4.2 Hz, 1H), 7.14 - 7.02 (m, 3H), 6.92 (dt, J = 6.8, 1.7 Hz, 1H), 6.23 (s, 1H), 1.09 (s, 12H), 0.53 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 165.85, 152.54, 149.16, 147.45, 139.24, 137.00, 135.99, 133.08, 129.59, 128.47, 127.87, 127.76, 126.07, 125.66, 120.86, 83.32, 24.73, -1.20. HRMS (ESI) calcd. For C 25 H 29 BClNO2Si[M + H] + : 450.1827. Found: 450.1826.

[0311] Example 18:

[0312] The reaction procedure was the same as Example 1 except that 2-methoxyphenylacetylene was used as the starting material. After purification, (E)-8-((l-(2-methoxyphenyl)-2- (4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)dimethylsilanyl)quinoline was obtained in 56% yield.

[0313] 1 H NMR (400 MHz, CDC13) δ 8.77 (dd, J = 4.2, 1.8 Hz, 1H), 8.02 (ddd, J = 10.1, 7.5, 1.7 Hz, 2H), 7.72 (dd, J = 8.1, 1.5 Hz, 1H), 7.47 (dd, J = 8.1, 6.8 Hz, 1H), 7.33 - 7.18 (m, 2H), 7.09 (ddd, J = 8.1, 7.4, 1.8 Hz, 1H), 6.89 (td, J = 7.4, 1.1 Hz, 1H), 6.64 (dd, J = 8.2, 1.1 Hz, 1H), 6.17 (s, 1H), 3.70 (s, 3H), 0.95 (s, 12H), 0.54 (s, 6H). 13C NMR (101 MHz, CDC13) δ 168.42, 155.18, 152.15, 148.59, 142.77, 139.56, 136.82, 135.66, 129.18, 128.37, 127.42, 127.18, 125.69, 120.66, 120.31, 108.85, 83.06, 54.71, 24.72, 0.20. HRMS (ESI) calcd. For C 26 H 32 BNO3Si[M + H] + : 446.2323. Found: 446.2327.

[0314] Example 19:

[0315] The reaction procedure was the same as Example 1, except that 2-fluorophenylacetylene was used as the starting material. After purification, (E)-8-((l-(2-fluorophenyl)-2- (4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)dimethylsilanyl)quinoline was obtained in 88% yield.

[0316] 1 H NMR (400 MHz, CDC13) δ 8.81 (dd, J = 4.2, 1.8 Hz, 1H), 8.07 (dd, J = 8.2, 1.8 Hz, 1H), 7.95 (dd, J = 6.8, 1.5 Hz, 1H), 7.80 (dd, J = 8.1, 1.5 Hz, 1H), 7.49 (dd, J = 8.1, 6.7 Hz, 1H), 7.31 (dd, J = 8.2, 4.2 Hz, 1H), 7.16 - 7.03 (m, 1H), 7.01 - 6.86 (m, 3H), 6.35 (s, 1H), 1.05 (s, 12H), 0.55 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 161.61, 158.84 (d, J = 242.6 Hz), 152.61, 149.01, 139.40, 136.95, 135.90, 132.90 (d, J = 17.4 Hz), 130.23 (d, J = 4.3 Hz), 129.41, 127.72, 127.18 (d, J = 7.7 Hz), 126.02, 122.84 (d, J = 3.3 Hz), 120.73, 114.55 (d, J = 22.6 Hz), 83.07, 24.64, -1.39. 19 F NMR (376 MHz, CDC13) δ -114.48. HRMS (ESI) calcd. For C 25H 29 BFNO2Si[M+H] + :434.2123.Found:434.2125.

[0317] Example 20:

[0318] The reaction procedure was the same as Example 1 except that 2-chlorostyrene was used as the starting material. After purification, (E)-8-((l-(2-chlorophenyl)-2- (4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)dimethylsilanyl)quinoline was obtained in 78% yield.

[0319] 1 H NMR (400 MHz, CDC13) δ 8.87 (dd, J = 4.1, 1.8 Hz, 1H), 8.14 (dd, J = 6.8, 1.5 Hz, 1H), 8.09 (dd, J = 8.2, 1.9 Hz, 1H), 7.79 (dd, J = 8.1, 1.5 Hz, 1H), 7.53 (dd, J = 8.1, 6.8 Hz, 1H), 7.40 (dd, J = 7.6, 1.7 Hz, 1H), 7.33 (dd, J = 8.2, 4.1 Hz, 1H), 7.30 (dd, J = 7.9, 1.2 Hz, 1H), 7.23 (td, J = 7.5, 1.3 Hz, 1H), 7.12 (td, J = 7.6, 1.7 Hz, 1H), 6.16 (s, 1H), 0.98 (s, 12H), 0.71 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 168.09, 152.13, 148.77, 148.61, 141.65, 137.39, 135.90, 131.00, 130.05, 128.73, 128.44, 127.55, 126.93, 126.23, 125.86, 120.49, 83.23, 24.71, 0.03. HRMS (ESI) calcd. For C 25 H 30 BClNO2Si[M+H] + :450.1827.Found:450.1825.

[0320] Example 21:

[0321] The reaction procedure was same as example 1 except that 2-ethynylbenzonitrile was used as starting material, after purification of the crude product, (E)-2-(l-(dimethyl(quinolin-8-yl)silyl)-2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2- yl)vinyl)benzonitrile was obtained in 72% yield.

[0322] 1 H NMR (400 MHz, CDC13 ) δ 8.88 (dd, J = 4.1, 1.8 Hz, 1H), 8.15 (d, J = 6.8 Hz, 1H), 8.08 (dd, J = 8.3, 1.8 Hz, 1H), 7.79 (d, J = 8.1 Hz, 1H), 7.55 (ddd, J = 21.0, 14.6, 7.7 Hz, 3H), 7.41 (t, J = 7.6 Hz, 1H), 7.32 (dd, J = 8.3, 4.1 Hz, 1H), 7.24 (t, J = 7.6 Hz, 1H), 6.23 (s, 1H), 0.93 (d, J = 7.4 Hz, 12H), 0.47 (d, J = 202.6 Hz, 6H). 13 C NMR (101 MHz, CDC13 ) δ 166.01, 152.38, 148.59, 140.87, 137.76, 136.08, 130.65, 129.59, 128.90, 127.71, 126.19 (q, J = 30.3 Hz) 125.94, 125.67 (q, J = 5.3 Hz), 125.51, 124.69 (q, J = 274.7 Hz), 120.57, 83.28, 24.78, 24.59, 0.44, -0.41. 19 FNMR (376 MHz, CDC13 ) δ -56.63. HRMS (ESI) calcd. For C 26 H 29 BF3NO2Si[M + H] + : 484.2091. Found: 484.2094.

[0323] Example 22:

[0324] The reaction procedure was same as example 1 except that 2-ethynylbenzonitrile was used as starting material, after purification of the crude product, (E)-2-(l-(dimethyl(quinolin-8-yl)silyl)-2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2- yl)vinyl)benzonitrile was obtained in 72% yield.

[0325] 1H NMR (400 MHz, CDC13) δ 8.83 (dd, J = 4.2, 1.8 Hz, 1H), 8.07 (dd, J = 6.8, 1.5 Hz, 1H), 8.03 (dd, J = 8.3, 1.8 Hz, 1H), 7.76 (dd, J = 8.2, 1.5 Hz, 1H), 7.53 - 7.44 (m, 2H), 7.42 - 7.33 (m, 2H), 7.29 (dd, J = 8.2, 4.2 Hz, 1H), 7.12 (td, J = 7.4, 1.5 Hz, 1H), 6.21 (s, 1H), 1.03 (s, 12H), 0.63 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 166.36, 154.29, 151.87, 148.71, 140.86, 137.33, 135.91, 132.08, 131.42, 129.04, 128.75, 127.47, 125.95, 125.75, 120.59, 119.34, 110.01, 83.48, 24.78, 0.31. HRMS (ESI) calcd. For C 26 H 29 BN2O2NaSi[M+Na] + : 463.1989. Found: 463.1989.

[0326] Example 23:

[0327] The reaction procedure was the same as Example 1, except that methyl 2-ethynylbenzoate was used as the starting material. After purification, methyl (E)-2-(l-(dimethyl(quinolin-8-yl)silyl)-2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)benzoate was obtained in 83% yield.

[0328] 1 H NMR (400 MHz, CDC13) δ 8.76 (d, J = 4.1 Hz, 0H), 8.08 (d, J = 8.3 Hz, 1H), 8.02 - 7.96 (m, 1H), 7.81 (t, J = 9.2 Hz, 1H), 7.54 - 7.48 (m, 2H), 7.29 (ddd, J = 14.4, 7.3, 3.4 Hz, 1H), 7.23 - 7.13 (m, 2H), 7.06 - 6.96 (m, 1H), 6.25 (s, 1H), 3.71 (d, J = 2.6 Hz, 3H), 0.96 (d, J = 10.0 Hz, 12H), 0.51 (d, J = 108.5 Hz, 6H). 13C NMR (101 MHz, CDC13) δ 168.86, 168.16, 148.87, 147.87, 140.18, 136.97, 135.94, 130.68, 129.66, 129.56, 129.29, 128.40, 127.83, 126.06, 125.28, 120.69, 82.79, 51.56, 24.64, 24.58, -0.73, -1.51. HRMS (ESI) calcd. For C 27 H 32 BNO4Si [M + H] + : 474.2272. Found: 474.2277.

[0329] Example 24:

[0330] The reaction procedure was the same as Example 1, except that 1-naphthalene acetylene was used as the starting material. After purification, (E)-8-(dimethyl(1-(naphthalen-2-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)silyl)quinoline was obtained in a yield of 69%.

[0331] 1 H NMR (400 MHz, CDC13) δ 8.86 (dd, J = 4.2, 1.8 Hz, 1H), 8.09 (dd, J = 8.3, 1.8 Hz, 1H), 7.96 (dd, J = 6.8, 1.5 Hz, 1H), 7.81 (dd, J = 8.2, 1.5 Hz, 1H), 7.79 - 7.74 (m, 1H), 7.71 - 7.67 (m, 1H), 7.64 (d, J = 8.4 Hz, 1H), 7.54 - 7.47 (m, 2H), 7.42 - 7.37 (m, 2H), 7.34 (dd, J = 8.2, 4.2 Hz, 1H), 7.26 (dd, J = 8.3, 1.8 Hz, 1H), 6.32 (s, 1H), 1.00 (s, 12H), 0.57 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 166.69, 152.70, 149.16, 143.48, 139.65, 137.18, 135.98, 133.27, 132.11, 129.48, 127.90, 127.79, 127.63, 127.05, 126.65, 126.09, 125.65, 125.55, 124.92, 83.18, 24.67, -1.02. HRMS (ESI) calcd. For C 29 H 32 BNO2Si [M + H]+ :466.2374.Found:466.2380.

[0332] Example 25:

[0333] The reaction procedure was similar to Example 1 except that 3,4-dichlorophenylacetylene was used as starting material. After purification, (E)-8-((l-(3,4-dichlorophenyl)-2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)dimethylsilanyl)quinoline was obtained in 66% yield.

[0334] 1 H NMR (400 MHz, CDC13) δ 8.83 (dd, J = 4.2, 1.8 Hz, 1H), 8.09 (dd, J = 8.2, 1.9 Hz, 1H), 7.84 (ddd, J = 21.3, 7.4, 1.5 Hz, 2H), 7.50 (dd, J = 8.1, 6.7 Hz, 1H), 7.34 (dd, J = 8.2, 4.2 Hz, 1H), 7.22 - 7.12 (m, 2H), 6.85 (dd, J = 8.2, 2.1 Hz, 1H), 6.23 (s, 1H), 1.09 (s, 12H), 0.53 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 165.32, 152.46, 149.17, 145.68, 139.00, 136.93, 136.05, 131.07, 129.77, 129.72, 129.37, 129.04, 127.80, 127.02, 126.10, 120.93, 83.40, 24.75, -1.26. HRMS (ESI) calcd. For C 25 H 29 BC12N02Si [M+H] + :484.1438.Found:484.1436.

[0335] Example 26:

[0336] The reaction procedure was similar to Example 1 except that 3,5-dimethoxyphenylacetylene was used as starting material. After purification, (E)-8-((l-(3,5-dimethoxyphenyl)-2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)dimethylsilanyl)quinoline was obtained in 55% yield.

[0337] 1H NMR (400 MHz, CDC13) δ 8.86 (dd, J = 4.2, 1.8 Hz, 1H), 8.08 (dd, J = 8.2, 1.9 Hz, 1H), 7.90 (dd, J = 6.8, 1.5 Hz, 1H), 7.79 (dd, J = 8.1, 1.5 Hz, 1H), 7.48 (dd, J = 8.1, 6.7 Hz, 1H), 7.33 (dd, J = 8.2, 4.2 Hz, 1H), 6.25 - 6.15 (m, 4H), 3.61 (s, 6H), 1.09 (s, 12H), 0.54 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 166.15, 159.86, 149.18, 147.67, 139.62, 137.15, 135.96, 129.42, 127.77, 126.06, 120.79, 105.73, 98.39, 83.23, 55.20, 24.73, -1.17. HRMS (ESI) calcd. For C 27 H 34 BNO4Si [M + H] + : 476.2428. Found: 476.2429.

[0338] Example 27:

[0339] The reaction procedure was the same as Example 1, except that 3,4- dimethoxyphenylacetylene was used as the starting material. After purification, (E)-8-((l-(3,4-dimethoxyphenyl)-2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2- yl)vinyl)dimethylsilanyl)quinoline was obtained in 69% yield.

[0340] 1 H NMR (400 MHz, CDC13) δ 8.86 (dd, J = 4.2, 1.8 Hz, 1H), 8.08 (dd, J = 8.2, 1.9 Hz, 1H), 7.90 (dd, J = 6.8, 1.5 Hz, 1H), 7.79 (dd, J = 8.1, 1.5 Hz, 1H), 7.48 (dd, J = 8.1, 6.7 Hz, 1H), 7.33 (dd, J = 8.2, 4.2 Hz, 1H), 6.25 - 6.15 (m, 4H), 3.61 (s, 6H), 1.09 (s, 12H), 0.54 (s, 6H). 13C NMR (101 MHz, CDC13) δ 166.13, 152.71, 149.17, 147.72, 147.25, 139.78, 138.40, 137.13, 135.96, 129.41, 127.76, 126.05, 120.78, 119.81, 111.36, 110.34, 83.19, 55.95, 55.50, 24.77, -1.12. HRMS (ESI) calcd. For C 27 H 34 BNO4Si[M + H] + : 476.2428. Found: 476.2428.

[0341] Example 28:

[0342] The reaction procedure was the same as Example 1, except that 3-ethynylpyridine was used as the starting material. After purification, (E)-8-(dimethyl(l-(pyridin-3-yl)-2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)silyl)quinoline was obtained in 78% yield.

[0343] 1 H NMR (400 MHz, CDC13) δ 8.79 (dd, J = 4.2, 1.8 Hz, 1H), 8.54 - 8.45 (m, 1H), 8.28 (dd, J = 4.9, 1.7 Hz, 1H), 8.07 - 7.95 (m, 2H), 7.77 (dd, J = 8.2, 1.5 Hz, 1H), 7.59 - 7.45 (m, 2H), 7.28 (dd, J = 8.5, 4.4 Hz, 1H), 7.02 (ddd, J = 7.8, 4.8, 0.8 Hz, 1H), 6.17 (s, 1H), 1.06 (s, 12H), 0.58 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 165.37, 151.76, 148.81, 147.78, 146.75, 145.33, 140.89, 136.92, 135.90, 134.15, 129.15, 127.50, 125.93, 122.05, 120.68, 83.44, 24.79, 0.31. HRMS (ESI) calcd. For C 24 H 29 BN2O2Si[M + H] + : 417.2170. Found: 417.2165.

[0344] Example 29:

[0345] The reaction procedure was the same as Example 1 except that 2-ethynylpyrazine was used as starting material. After purification of the crude product, (E)-8-(dimethyl(1-(pyrazin-2-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)silyl)quinoline was obtained in 56% yield.

[0346] 1 H NMR (400 MHz, CDC13) δ 8.70 (dd, J = 4.2, 1.8 Hz, 1H), 8.59 (d, J = 1.5 Hz, 1H), 8.17 (dd, J = 2.6, 1.5 Hz, 1H), 8.14 (d, J = 2.6 Hz, 1H), 8.00 (ddd, J = 8.2, 3.5, 1.7 Hz, 2H), 7.74 (dd, J = 8.1, 1.5 Hz, 1H), 7.50 (dd, J = 8.1, 6.8 Hz, 1H), 7.24 (dd, J = 8.2, 4.2 Hz, 1H), 6.35 (s, 1H), 1.10 (s, 12H), 0.66 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 164.69, 162.83, 151.61, 148.80, 143.51, 141.91, 141.31, 141.16, 136.77, 135.84, 128.96, 127.44, 126.01, 120.59, 83.63, 24.83, 0.07. HRMS (ESI) calcd. For C 23 H 28 BN302Si [M+H] + : 418.2122. Found: 418.2123.

[0347] Example 30:

[0348] The reaction procedure was the same as Example 1 except that 5-ethynylpyrimidine was used as starting material. After purification of the crude product, (E)-8-(dimethyl(1-(pyrimidin-2-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)silyl)quinoline was obtained in 73% yield.

[0349] 1H NMR (400 MHz, CDC13) δ 8.84 (s, 1H), 8.77 (dd, J = 4.2, 1.8 Hz, 1H), 8.57 (s, 2H), 8.07 - 7.95 (m, 2H), 7.78 (dd, J = 8.1, 1.5 Hz, 1H), 7.51 (dd, J = 8.1, 6.8 Hz, 1H), 7.35 - 7.24 (m, 1H), 6.18 (s, 1H), 1.12 (s, 12H), 0.63 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 161.77, 155.99, 154.25, 151.41, 148.89, 142.86, 140.10, 136.94, 136.04, 129.52, 127.51, 126.02, 120.81, 83.69, 24.82, 0.04. HRMS (ESI) calcd. For C 23 H 28 BN3O2Si[M + H] + : 418.2122. Found: 418.2116.

[0350] Example 31:

[0351] The reaction procedure was the same as Example 1, except that 2-ethynylthiophene was used as the starting material, and after purification, (E)-8-(dimethyl(2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-l-(thiophen-2-yl)vinyl)silyl)quinoline was obtained in 81% yield.

[0352] 1 H NMR (400 MHz, CDC13) δ 8.84 (s, 1H), 8.77 (dd, J = 4.2, 1.8 Hz, 1H), 8.57 (s, 2H), 8.07 - 7.95 (m, 2H), 7.78 (dd, J = 8.1, 1.5 Hz, 1H), 7.51 (dd, J = 8.1, 6.8 Hz, 1H), 7.35 - 7.24 (m, 1H), 6.18 (s, 1H), 1.12 (s, 12H), 0.63 (s, 6H). 13C NMR (101 MHz, CDC13) δ 158.92, 152.29, 148.87, 147.02, 141.32, 137.04, 135.87, 128.97, 127.59, 126.76, 126.00, 124.84, 123.58, 120.65, 83.36, 24.84, -0.84. HRMS (ESI) calcd. For C 23 H 28 BNO2SSi[M + H] + : 422.1781. Found: 422.1785.

[0353] Example 32:

[0354] The reaction procedure was the same as Example 1, except that 1,4-diethynylbenzene was used as the starting material, and the molar equivalent of TBSQ was twice as much as that of the starting material. After purification, 1,4-bis[((E)-1-(dimethyl(quinolin-8-yl)silyl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)]benzene was obtained in 81% yield.

[0355] 1 H NMR (400 MHz, CDC13) δ 8.77 (dd, J = 4.1, 1.8 Hz, 2H), 8.05 - 7.94 (m, 4H), 7.73 (dd, J = 8.1, 1.5 Hz, 2H), 7.46 (dd, J = 8.1, 6.7 Hz, 2H), 7.34 - 7.20 (m, 2H), 6.99 (s, 4H), 6.18 (s, 2H), 1.01 (s, 24H), 0.51 (s, 12H). 13 C NMR (101 MHz, CDC13) δ 169.19, 152.15, 148.69, 147.18, 141.87, 136.97, 135.80, 128.76, 127.51, 125.86, 125.79, 120.49, 83.10, 24.77, 0.75. HRMS (ESI) calcd. For C 44 H 55 B2N2O4SSi[M + H] + : 753.3886. Found: 753.3896.

[0356] Example 33:

[0357] The reaction procedure was the same as Example 1 except that (E)-1-buten-3- ynylbenzene was used as starting material. After purification of the crude product, (E)-8- (dimethyl((1E,3E)-4-phenyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)buta-1,3- dien-2-yl)silyl)quinoline was obtained in 72% yield.

[0358] 1 H NMR (400 MHz, CDC13) δ 8.92 (dd, J = 4.2, 2.0 Hz, 1H), 8.13 (dd, J = 8.3, 2.0 Hz, 1H), 8.04 - 7.93 (m, 2H), 7.83 (dd, J = 8.2, 1.7 Hz, 1H), 7.50 (td, J = 7.5, 6.6, 1.7 Hz, 1H), 7.42 - 7.34 (m, 1H), 7.33 - 7.23 (m, 4H), 7.22 - 7.15 (m, 1H), 6.68 (d, J = 16.5 Hz, 1H), 6.22 (s, 1H), 1.38 (s, 12H), 0.72 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 163.69, 152.74, 149.22, 140.10, 138.26, 137.50, 136.09, 134.14, 133.43, 129.41, 128.55, 127.82, 127.40, 126.61, 126.19, 120.81, 83.34, 25.17, -0.21. HRMS (ESI) calcd. For C 27 H 33 BNO2Si[M + H] + : 442.2374. Found: 442.2371.

[0359] Example 34:

[0360] The reaction procedure was the same as Example 1 except that 1-ethynyl-1- cyclohexene was used as starting material. After purification of the crude product, (E)-8- (dimethyl(1-(cyclohex-1-en-1-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)silyl)quinoline was obtained in 74% yield.

[0361] 1H NMR (400 MHz, CDC13) δ 8.83 (dd, J = 4.2, 1.8 Hz, 1H), 8.07 (dd, J = 8.2, 1.9 Hz, 1H), 7.94 (dd, J = 6.8, 1.5 Hz, 1H), 7.76 (dd, J = 8.1, 1.5 Hz, 1H), 7.47 (dd, J = 8.1, 6.8 Hz, 1H), 7.31 (dd, J = 8.2, 4.1 Hz, 1H), 6.08 (s, 1H), 5.49 - 4.70 (m, 1H), 2.09 (dt, J = 4.6, 2.2 Hz, 2H), 1.92 - 1.50 (m, 2H), 1.36 (qd, J = 4.5, 1.7 Hz, 4H), 1.03 (s, 12H), 0.63 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 171.85, 152.38, 148.74, 145.70, 142.39, 136.79, 135.81, 128.61, 127.56, 125.92, 120.97, 120.47, 83.04, 29.12, 25.30, 24.82, 23.03, 22.31, 0.66. HRMS (ESI) calcd. For C 25 H 35 BNO2Si[M + H] + : 420.2503. Found: 420.2537.

[0362] Example 35:

[0363] The reaction procedure was the same as Example 1, except that 1-ethynylcyclohexane was used as the starting material, and the molar equivalent was increased to 5 equivalents. After purification, (E)-8-(dimethyl(l-cyclohexyl-2-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)vinyl)silol was obtained in a yield of 54%. 1 H NMR (400 MHz, CDC13) δ 8.82 (dd, J = 4.2, 1.9 Hz, 1H), 8.07 (dd, J = 8.3, 1.9 Hz, 1H), 7.96 - 7.89 (m, 1H), 7.79 - 7.72 (m, 1H), 7.50 - 7.43 (m, 1H), 7.30 (dt, J = 7.9, 3.9 Hz, 1H), 6.13 (s, 1H), 2.42 (s, 1H), 1.75 - 1.71 (m, 4H), 1.63 - 1.61 (m, 2H), 1.17 - 1.12 (m, 4H), 0.99 (s, 12H), 0.61 (s, 6H). 13C NMR (101 MHz, CDC13) δ 174.37, 152.47, 148.78, 142.24, 136.98, 135.90, 128.57, 127.58, 125.88, 120.49, 82.87, 46.22, 33.38, 27.26, 26.63, 24.81, 0.30. HRMS (ESI) calcd. For C 25 H 37 BNO2Si [M + H] + : 422.2687. Found: 422.2688.

[0364] Example 36:

[0365] The reaction procedure was the same as Example 1, except that tert-butyl acetylene was used as starting material, and the molar equivalent was increased to 5 equivalents. After purification, (E)-8-(dimethyl(3,3-dimethyl-l-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)but-l-en-2-yl)silyl)quinoline was obtained in 65% yield.

[0366] 1 H NMR (400 MHz, CDC13) δ 8.83 (dd, J = 4.2, 1.9 Hz, 1H), 8.04 (dd, J = 8.3, 1.9 Hz, 1H), 7.93 (dd, J = 6.8, 1.5 Hz, 1H), 7.73 (dd, J = 8.1, 1.5 Hz, 1H), 7.45 (dd, J = 8.1, 6.8 Hz, 1H), 7.29 (dd, J = 8.2, 4.1 Hz, 1H), 6.22 (s, 1H), 1.24 (s, 9H), 0.78 (s, 12H), 0.73 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 174.34, 152.45, 148.56, 143.64, 137.21, 135.78, 128.48, 127.67, 126.00, 120.43, 82.77, 40.72, 30.26, 24.63, 3.87. HRMS (ESI) calcd. For C 23 H 34 BNO2Si [M + H] + : 396.2530. Found: 396.2527.

[0367] Example 37:

[0368] The reaction procedure was the same as Example 1 except that 4-phenyl-1- butyne was used as the starting material and the molar equivalent was increased to 5 equivalents. After purification of the crude product, (E)-8-(dimethyl(4-phenyl-1-(4,4,5,5- tetramethyl-1,3,2-dioxaborolan-2-yl)but-1-en-2-yl)silyl)quinoline was obtained in a yield of 63%.

[0369] 1 H NMR (400 MHz, CDC13) δ 8.89 (dd, J = 4.0, 1.8 Hz, 1H), 8.13 (dt, J = 8.4, 1.6 Hz, 1H), 8.04 (dd, J = 6.7, 1.6 Hz, 1H), 7.85 (d, J = 8.0 Hz, 1H), 7.62 - 7.52 (m, 1H), 7.36 (ddd, J = 8.3, 4.2, 1.2 Hz, 1H), 7.29 - 7.22 (m, 2H), 7.20 - 7.15 (m, 1H), 7.01 (d, J = 7.4 Hz, 2H), 6.27 (d, J = 1.4 Hz, 1H), 2.79 - 2.64 (m, 4H), 1.13 (s, 12H), 0.73 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 168.87, 152.47, 148.97, 142.96, 141.66, 137.01, 135.97, 128.88, 128.41, 128.29, 127.70, 125.96, 125.62, 120.64, 83.04, 44.99, 36.66, 24.84, 0.07. HRMS (ESI) calcd. For C 27 H 34 BNO2Si[M + H] + : 444.2530. Found: 444.2534.

[0370] Example 38:

[0371] The reaction procedure was the same as Example 1 except that 4-chloro-1- butyne was used as the starting material and the molar equivalent was increased to 5 equivalents. After purification of the crude product, (E)-8-(dimethyl(5-chloro-1-(4,4,5,5- tetramethyl-1,3,2-dioxaborolan-2-yl)pent-1-en-2-yl)silyl)quinoline was obtained in a yield of 57%. 1H NMR (400 MHz, CDC13) δ 8.84 (dd, J = 4.2, 1.8 Hz, 1H), 8.08 (dd, J = 8.2, 1.8 Hz, 1H), 7.94 (dd, J = 6.8, 1.5 Hz, 1H), 7.79 (dd, J = 8.1, 1.5 Hz, 1H), 7.49 (dd, J = 8.1, 6.8 Hz, 1H), 7.32 (dd, J = 8.3, 4.2 Hz, 1H), 6.09 (t, J = 1.4 Hz, 1H), 3.45 (t, J = 6.8 Hz, 2H), 2.58 - 2.40 (m, 2H), 1.99 - 1.85 (m, 2H), 1.04 (s, 12H), 0.62 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 167.43, 152.35, 148.92, 141.48, 136.95, 136.00, 128.90, 127.67, 125.94, 120.65, 83.06, 45.03, 39.45, 32.30, 24.80, -0.07. HRMS (ESI) calcd. For C 22 H 32 BClNO2Si [M+H] + : 416.1984. Found: 416.1979.

[0372] Example 39:

[0373] The reaction procedure was the same as Example 1, except that (1R,2S,5R)-2- isopropyl-5-methylcyclohexyl 4-ethynylbenzoate was used as the starting material, and (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl 4-((E)-1-(dimethyl(quinolin-8- yl)silyl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)benzoate was obtained in 50% yield after purification of the crude product.

[0374] 1H NMR (400 MHz, CDC13) δ 8.84 - 8.81 (dd, 1H), 8.09 (d, J = 8.2 Hz, 1H), 7.89 (d, J = 6.8 Hz, 1H), 7.82 (t, J = 8.0 Hz, 3H), 7.48 (t, J = 7.4 Hz, 1H), 7.33 (dd, J = 8.3, 4.2 Hz, 1H), 7.09 (d, J = 7.9 Hz, 2H), 6.25 (s, 1H), 4.89 (td, J = 10.8, 4.3 Hz, 1H), 2.13 (d, J = 12.2 Hz, 1H), 1.99 - 1.87 (m, 1H), 1.80 - 1.67 (m, 2H), 1.63 - 1.46 (m, 3H), 1.33 - 1.23 (m, 1H), 1.04 (s, 12H), 0.91 (t, J = 7.2 Hz, 7H), 0.78 (d, J = 6.9 Hz, 3H), 0.52 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 166.65 (d, J = 3.7 Hz), 152.59, 150.75, 149.15, 139.18, 137.04, 135.99, 129.60, 128.72, 128.08, 127.79, 127.55, 126.07, 120.85, 83.29, 74.63, 47.45, 41.16, 34.52, 31.58, 26.76, 24.67, 23.99, 22.20, 20.85, 16.86, -1.24. HRMS (ESI) calcd. For C 36 H 49 BNO4Si[M + H] + : 598.3524. Found: 598.3526.

[0375] Example 40:

[0376] The reaction procedure was the same as Example 1, except that (8R,9S,13S,14S)-3-ethynyl-13-methyl-6,7,8,9,11,12,13,14,15,16-decahydro-17H- cyclopenta[a]phenanthren-17-one was used as the starting material. After purification, (8R,9S,13S,14S)-3-((E)-1-(dimethyl(quinolin-8-yl)silyl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)-13-methyl-6,7,8,9,11,12,13,14,15,16-decahydro-17H-cyclopenta[a]phenanthren-17-one was obtained in 54% yield.

[0377] 1H NMR (400 MHz, CDC13) δ 8.85 (dd, J = 4.2, 1.8 Hz, 1H), 8.08 (dd, J = 8.3, 1.8 Hz, 1H), 7.94 (dd, J = 6.7, 1.5 Hz, 1H), 7.80 (dd, J = 8.2, 1.5 Hz, 1H), 7.48 (dd, J = 8.1, 6.8 Hz, 1H), 7.32 (dd, J = 8.3, 4.2 Hz, 1H), 7.07 (d, J = 8.0 Hz, 1H), 6.89 (dd, J = 8.0, 1.9 Hz, 1H), 6.81 (d, J = 1.9 Hz, 1H), 6.19 (s, 1H), 2.78 (dt, J = 8.0, 4.5 Hz, 2H), 2.49 (dd, J = 18.8, 8.6 Hz, 1H), 2.38 (p, J = 4.2 Hz, 1H), 2.26 (td, J = 10.3, 4.6 Hz, 1H), 2.20 - 2.01 (m, 2H), 1.94 (dd, J = 8.4, 2.8 Hz, 2H), 1.72 - 1.22 (m, 6H), 1.10 (s, 12H), 0.90 (s, 3H), 0.54 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 221.13, 165.94, 152.75, 149.08, 142.76, 139.94, 137.28, 137.21, 135.94, 135.00, 129.34, 128.27, 127.77, 126.04, 125.32, 124.24, 120.72, 83.14, 50.71, 48.14, 44.49, 38.49, 36.00, 31.77, 29.56, 26.75, 25.88, 24.75 (d, J = 2.4 Hz), 21.72, 14.00, -0.94. HRMS (ESI) calcd. For C 37 H 47 BNO3Si[M + H] + : 592.3418. Found: 592.3419.

[0378] The present application also provides the trans-1-boronyl-2-silyl olefins generated in the above examples 1-40 as important synthetic building blocks, which are applied as follows:

[0379] Application Example 1:

[0380] Compound C-1, compound 2, ligand, additive are reacted in a solvent under the action of a palladium catalyst to obtain a compound shown in compound 3;

[0381] Compound C-1 is Compound 2 is Compound 3 is

[0382] The specific implementation steps are as follows:

[0383] Under argon protection, Pd(OAc)₂ (2.2 mg, 10 mol%) and P( t A mixture of Bu2Me (3.2 mg, 20 mol%), NaOH (12.0 mg, 0.30 mmol), compound C-1 (0.10 mmol, 49.1 mg), and compound 2 (0.20 mmol, 42.6 mg) dissolved in anhydrous dioxane (1.0 mL) was reacted with vigorous stirring at 60 °C for 24 hours. After the reaction mixture cooled to room temperature, it was filtered through a short silica gel column (eluted with ethyl acetate) to remove the catalyst and inorganic salts. The filtrate was concentrated and purified by silica gel column chromatography (n-hexane:ethyl acetate = 20:1) to obtain compound 3 (36.7 mg, yield 74%) as a colorless solid.

[0384] 1 H NMR (400MHz, CDCl3) δ8.87(dt,J=4.5,2.0Hz,1H),8.14(dd,J=8.2,2.2Hz,1H),7.98(d,J=6.7Hz,1H),7.86(d ,J=8.1Hz,1H),7.70–7.59(m,2H),7.58–7.51(m,1H),7.51–7.46(m,2H),7.46–7.40(m,2H),7.39–7.32(m,2H ),7.31–7.26(m,2H),7.24–7.16(m,1H),7.13(d,J=7.5Hz,2H),7.06–6.99(m,2H),6.15(td,J=7.1,2.0Hz,1H ),2.54(t,J=7.8Hz,2H),2.12(qd,J=7.1,2.0Hz,2H),1.62–1.51(m,3H),1.42(p,J=7.5Hz,2H),0.56(s,6H). 13C NMR (101 MHz, CDC13) δ 152.74, 149.03, 143.28, 142.98, 142.86, 142.23, 141.31, 140.28, 137.76, 137.06, 136.01, 129.37, 128.78, 128.52, 128.31, 127.80, 126.97, 126.42, 126.04, 125.65, 120.75, 35.80, 30.82, 30.02, 29.16, -1.16. HRMS (ESI) calcd. For C 35 H 36 NSi[M+H] + :498.2617. Found:498.2618.

[0385] Application Example 2

[0386] Compound C-1, compound 4, additive are reacted in the presence of a palladium catalyst in a solvent to obtain a compound as shown in compound 5 or compound 6;

[0387] wherein compound 4 is compound 5 is compound 6 is Compound C-1 is the same as compound C-1 in application example 1, the following application examples are also the same, and will not be repeated.

[0388] The specific implementation steps are as follows:

[0389] Compound C-1 (49.1 mg, 0.1 mmol), compound 4 (28.1 mg, 0.12 mmol or 46.8 mg, 0.2 mmol) and PdCl2dppf (7.3 mg, 0.01 mmol) were added to a dry pressure tube under argon protection and dissolved in anhydrous tetrahydrofuran (0.75 mL). Potassium hydroxide (16.8 mg, 0.30 mmol) and water (0.25 mL) were added to the mixed system at room temperature. After sealing the reaction tube, it was heated to 70°C and stirred for 24 hours. After the reaction solution was quenched with water (2 mL), it was extracted with ethyl acetate (10 mL x 3). The combined organic phase was dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation under reduced pressure. The residue was separated and purified by silica gel column chromatography (n-hexane: ethyl acetate = 20: 1) to obtain compound 5 (41.9 mg, yield 89%) or compound 6 (47.3 mg, yield 82%) as a white solid.

[0390] Compound 5: 1H NMR (400 MHz, CDC13) δ 8.93 (dd, J = 4.2, 1.9 Hz, 1H), 8.13 (dd, J = 8.2, 1.8 Hz, 1H), 8.07 - 8.00 (m, 1H), 7.89 - 7.82 (m, 1H), 7.69 - 7.62 (m, 2H), 7.57 - 7.50 (m, 3H), 7.45 (t, J = 7.5 Hz, 2H), 7.39 - 7.31 (m, 2H), 7.11 (d, J = 7.9 Hz, 2H), 7.02 - 6.93 (m, 3H), 6.69 - 6.62 (m, 2H), 3.72 (s, 3H), 0.64 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 158.59, 152.78, 149.13, 142.94, 142.76, 141.12, 139.93, 138.62, 137.90, 137.20, 136.03, 130.98, 130.71, 129.49, 128.82, 128.50, 127.83, 127.04, 126.87, 126.07, 120.79, 113.40, 55.22, -1.20. HRMS (ESI) calcd. For C 32 H 30 NOSi[M + H] + : 472.2097. Found: 472.2089.

[0391] Compound 6: 1 H NMR (400 MHz, CDC13) δ 8.95 (dd, J = 4.2, 1.8 Hz, 1H), 8.08 (dd, J = 8.2, 1.8 Hz, 1H), 7.68 (dd, J = 8.0, 1.5 Hz, 1H), 7.65 - 7.57 (m, 2H), 7.46 - 7.38 (m, 5H), 7.38 - 7.34 (m, 1H), 7.33 - 7.27 (m, 4H), 6.86 - 6.77 (m, 2H), 6.61 - 6.52 (m, 2H), 6.51 - 6.43 (m, 2H), 6.35 - 6.27 (m, 2H), 3.70 (s, 3H), 3.61 (s, 3H), 0.30 (s, 6H). 13C NMR (101 MHz, CDC13) δ 158.17, 157.50, 152.01, 151.71, 148.55, 144.38, 142.84, 141.67, 141.37, 137.19, 136.78, 136.27, 135.82, 135.47, 131.10, 130.52, 130.50, 128.76, 128.36, 127.50, 126.91, 126.88, 125.99, 125.97, 120.63, 112.59, 112.48, 55.20, 55.06, 0.51. HRMS (ESI) calcd. For C 39 H 36 NO2Si[M + H] + : 578.2515. Found: 578.2512.

[0392] Example 3:

[0393] Compound C-1, copper acetate, in a solvent to obtain a compound shown in formula 7; wherein, formula 7 is

[0394] The specific implementation steps are as follows:

[0395] In a 8 mL vial, compound C-1 (49.1 mg, 0.1 mmol), copper acetate (18.2 mg, 0.1 mmol), N,N-dimethylformamide (1 mL) and ethanol (0.2 mL) were added, and stirred at 60 °C for 8 hours, then quenched with 1M hydrochloric acid solution (3 mL). The reaction solution was extracted with diethyl ether (5 mL x 3), and the combined organic layer was washed with sodium bicarbonate solution and saturated brine, dried over anhydrous sodium sulfate and concentrated. Finally, formula 7 (34.9 mg, yield 48%) was obtained by column chromatography separation and purification.

[0396] 1 H NMR (400 MHz, CDC13) δ 8.90 (dd, J = 4.2, 1.9 Hz, 2H), 8.13 (dd, J = 8.3, 1.9 Hz, 2H), 7.95 (dd, J = 6.8, 1.5 Hz, 2H), 7.85 (dd, J = 8.1, 1.6 Hz, 2H), 7.60 - 7.55 (m, 4H), 7.55 - 7.49 (m, 4H), 7.45 (dd, J = 8.4, 6.6 Hz, 5H), 7.42 - 7.35 (m, 5H), 7.34 - 7.28 (m, 2H), 7.19 - 7.11 (m, 4H), 0.60 (s, 12H). 13C NMR (101 MHz, CDC13) δ 168.39, 152.62, 149.27, 141.13, 139.72, 139.27, 138.54, 137.58, 137.17, 136.14, 129.78, 129.26, 128.83, 127.15, 127.02, 126.54, 126.17, 122.33, 120.95, 1.17. HRMS (MALDI) calcd. For C 50 H 45 N2Si2[M+H] + : 729.3121. Found: 729.3128.

[0397] Example 4:

[0398] Compound C-1, copper bromide, in a solvent, under a protective atmosphere, to obtain a compound shown in formula 8; wherein formula 8 is

[0399]

[0400] The specific implementation steps are as follows:

[0401] Under argon protection, compound C-1 (0.1 mmol, 1.0 equivalent, 49.1 mg), copper bromide (0.3 mmol, 3.0 equivalents, 5.95 mg), methanol (0.5 mL) and water (0.5 mL) were added to a 10 mL round-bottom flask (operation in the glove box). After sealing the reaction bottle, it was removed from the glove box and heated in an oil bath at 80°C for 6 hours. The reaction solution was diluted with water and extracted with diethyl ether three times (3 x 5 mL). The organic phase was combined and dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was separated and purified by silica gel flash column chromatography to obtain a colorless oil product formula 8 (23.4 mg, yield 53%).

[0402] 1 H NMR (400 MHz, CDC13) δ 8.92 (dd, J = 4.2, 1.8 Hz, 1H), 8.15 (dd, J = 8.3, 1.8 Hz, 1H), 7.90 (ddd, J = 17.1, 7.4, 1.5 Hz, 2H), 7.64 - 7.57 (m, 2H), 7.57 - 7.48 (m, 3H), 7.47 - 7.37 (m, 3H), 7.37 - 7.28 (m, 1H), 7.10 - 7.04 (m, 2H), 6.78 (s, 1H), 0.59 (s, 6H). 13C NMR (101 MHz, CDC13) δ 152.47, 149.39, 148.88, 141.03, 140.54, 139.03, 138.09, 137.06, 136.17, 130.04, 128.81, 128.05, 127.87, 127.20, 127.07, 126.79, 126.15, 121.08, 115.50, -1.12. HRMS (ESI) calcd. For C 25 H 23 BrNSi[M+H] + : 444.0783. Found: 444.0780.

[0403] Example 5:

[0404] In a protective atmosphere, compound C-1, sodium azide is reacted in the presence of a copper catalyst in a solvent to obtain a compound shown in formula 9; wherein formula 9 is

[0405] The specific implementation steps are as follows:

[0406] Under argon protection, sodium azide (0.15 mmol, 1.5 equivalents) and anhydrous copper sulfate (9.6 mg, 0.06 mmol, 0.6 equivalents) were added to an oven-dried 4 mL reaction bottle, and then a methanol solution (1 mL) of compound C-1 (49.1 mg, 0.1 mmol) was slowly added dropwise. After stirring the mixture for 5 hours, it was concentrated under reduced pressure. The residue was purified by silica gel flash column chromatography (eluent: n-hexane / ethyl acetate = 30:1) to obtain the target product formula 9 (36.9 mg, yield 91%) as a colorless oil.

[0407] 1 H NMR (400 MHz, CDC13) δ 8.93 (dd, J = 4.4, 1.8 Hz, 1H), 8.16 (dd, J = 8.3, 1.8 Hz, 1H), 7.95 (dd, J = 6.9, 1.4 Hz, 1H), 7.88 (d, J = 8.2 Hz, 1H), 7.62 - 7.46 (m, 5H), 7.46 - 7.38 (m, 3H), 7.32 (t, J = 7.4 Hz, 1H), 7.14 (d, J = 8.0 Hz, 2H), 6.64 (s, 1H), 0.59 (s, 6H). 13C NMR (101 MHz, CDC13) δ 152.54, 149.30, 141.10, 138.97, 138.85, 138.50, 137.10, 136.20, 133.38, 131.18, 129.87, 128.92, 128.77, 127.88, 127.12, 127.06, 126.70, 126.16, 121.01, -1.11. HRMS (ESI) calcd. For C 25 H 23 N4Si[M+H] + : 407.1692. Found: 407.1679.

[0408] Example 6:

[0409] Compound C-1, compound 10, under the action of a rhodium catalyst, in a solvent, to obtain a compound represented by compound 11;

[0410] Compound 10 is Compound 11 is

[0411] The specific implementation steps are as follows:

[0412] Into an 8 mL reaction bottle was added compound C-1 (98.2 mg, 0.2 mmol), compound 10 (62.3 mg, 0.3 mmol), [Rh(cod)Cl]2(3.0 mg, 3 mol%), methanol (1 mL) and water (0.2 mL). The reaction bottle was sealed after being bubbled with nitrogen for 10 seconds, and the mixture was stirred at 100°C for 18 hours. After cooling to room temperature, it was concentrated under reduced pressure. The residue was purified by silica gel flash column chromatography (eluent: n-hexane / ethyl acetate = 20:1) to obtain the target product compound 11 (102 mg, yield 89%) as a colorless oil.

[0413] 1H NMR (400 MHz, CDC13) δ 8.79 (dd, J = 4.2, 1.9 Hz, 1H), 8.12 (dd, J = 8.3, 1.9 Hz, 1H), 7.92 - 7.72 (m, 4H), 7.65 - 7.56 (m, 2H), 7.54 - 7.47 (m, 2H), 7.47 - 7.41 (m, 3H), 7.40 - 7.31 (m, 5H), 7.30 - 7.23 (m, 2H), 7.23 - 7.17 (m, 1H), 7.17 - 7.11 (m, 2H), 6.93 - 6.79 (m, 2H), 6.31 (d, J = 9.6 Hz, 1H), 4.21 (dt, J = 9.8, 7.3 Hz, 1H), 3.30 (d, J = 7.3 Hz, 2H), 0.50 (d, J = 7.5 Hz, 6H). 13 C NMR (101 MHz, CDC13) δ 198.53, 152.65, 148.96, 144.00, 143.74, 143.68, 141.39, 141.27, 139.62, 137.99, 137.13, 137.08, 135.96, 132.90, 129.42, 128.78, 128.57, 128.40, 128.33, 127.72, 127.51, 126.97, 126.47, 126.26, 126.04, 120.72, 45.80, 42.19, -1.52, -1.55. HRMS (ESI) calcd. For C 40 H 36 NOSi[M + H] + : 574.2566. Found: 574.2569.

[0414] Application Example 7:

[0415] Compound 5 (Compound 5 is the compound 5 of Application Example 2, the following application examples relating to Compound 5 are the same case, and the subsequent will not be repeated), tetrabutylammonium fluoride, in a solvent, to obtain the compound shown in compound 12;

[0416] Compound 12 is

[0417] The specific implementation steps are as follows:

[0418] Into an 8 mL reaction vial was placed compound 5 (47.1 mg, 0.1 mmol), tetrahydrofuran (1 mL) and a solution of tetrabutylammonium fluoride (0.2 mL, 1.0 M in THF). The reaction mixture was stirred at room temperature for 12 hours before being concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel (eluent: n-hexane / ethyl acetate = 30:1) to give the target compound 12 as a colorless oil (26.3 mg, yield 92%).

[0419] 1 H NMR (400 MHz, CDC13) δ 7.58 (d, J = 7.7 Hz, 2H), 7.47 (dd, J = 8.4, 2.2 Hz, 2H), 7.44 - 7.37 (m, 2H), 7.36 - 7.28 (m, 3H), 7.26 - 7.20 (m, 2H), 6.81 - 6.73 (m, 2H), 6.60 - 6.48 (m, 2H), 3.78 (s, 3H). 13 C NMR (101 MHz, CDC13) δ 158.91, 140.89, 139.72, 136.77, 130.32, 130.12, 129.89, 129.42, 128.90, 128.50, 127.38, 127.03, 126.98, 113.81, 55.35. HRMS (EI) calcd. For C 21 H 18 O[M] + : 286.1358. Found: 286.1353.

[0420] Application Example 8:

[0421] Compound 5, 18-crown-6, potassium tert-butoxide, heavy water, in a solvent, under a protective atmosphere, to obtain a compound shown as compound 13;

[0422] wherein the compound 13 is

[0423] The molar ratio of the compound 5, 18-crown-6, potassium tert-butoxide, heavy water is 1:2:2:10; and / or,

[0424] The concentration of the compound 5 in the solvent is 0.1 mol / L; and / or,

[0425] The reaction temperature is 60°C; and / or,

[0426] The reaction time is 12 hours;

[0427] The specific implementation steps are as follows:

[0428] To an 8 mL reaction vial was added compound 5 (47.1 mg, 0.1 mmol), 18-crown-6 (52.8 mg, 0.2 mmol), potassium tert-butoxide (22.4 mg, 0.2 mmol), tetrahydrofuran (1 mL), and heavy water (20 mg, 1.0 mmol). The reaction vial was sealed after being bubbled with nitrogen for 10 seconds, and the mixture was stirred at 60 °C for 12 hours, followed by concentration under reduced pressure. The residue was purified by flash column chromatography on silica gel (eluent: n-hexane / ethyl acetate = 30:1) to give the target product compound 13 (24.6 mg, yield 86%, deuterium enrichment 90%) as a colorless oil.

[0429] 1 H NMR (400 MHz, CDC13) δ 7.54 (d, J = 7.6 Hz, 2H), 7.46 - 7.33 (m, 4H), 7.29 (dd, J = 6.8, 4.7 Hz, 3H), 7.21 - 7.16 (m, 2H), 6.77 - 6.69 (m, 2H), 6.51 (s, 1H), 3.74 (s, 3H). 13 C NMR (101 MHz, CDC13) δ 158.87, 140.87, 139.70, 136.66, 130.31, 130.10, 129.98, 129.86, 129.41, 128.90, 127.38, 127.02, 126.97, 113.79, 55.37. HRMS (EI) calcd. For C 21 H 17 DO[M] + : 287.1420. Found: 287.1417.

[0430] Application Example 9:

[0431] Compound 5, m-chloroperoxybenzoic acid, sodium bicarbonate, in a solvent, to give a compound represented by compound 14;

[0432] wherein compound 14 is

[0433] The specific implementation steps are as follows:

[0434] To a solution of compound 5 (47.1 mg, 0.1 mmol) and sodium bicarbonate (20.16 mg, 0.24 mmol) in dichloromethane (2.0 mL) was added m-chloroperoxybenzoic acid (19 mg, 0.11 mmol) under argon atmosphere. The resulting mixture was stirred at room temperature for 12 h. The reaction was quenched with 5% aqueous sodium sulfite solution and extracted with diethyl ether. The organic phase was washed with saturated sodium chloride solution, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was separated and purified by preparative thin layer chromatography on silica gel (eluent: n-hexane / ethyl acetate = 20:1) to give compound 14 (20.8 mg, yield 66%) as a colorless oil.

[0435] 1 H NMR (400 MHz, CDC13) δ 8.05 (dd, J = 8.4, 1.9 Hz, 2H), 8.01 - 7.95 (m, 2H), 7.72 (dd, J = 8.4, 1.9 Hz, 2H), 7.66 - 7.60 (m, 2H), 7.51 - 7.41 (m, 3H), 7.05 - 6.95 (m, 2H), 3.89 (s, 3H). 13 C NMR (101 MHz, CDC13) δ 194.58, 193.29, 165.15, 147.58, 139.71, 132.58, 130.63, 129.17, 128.73, 127.74, 127.50, 127.40, 126.28, 114.52, 55.82. HRMS (ESI) calcd. For C 21 H 16 NaO3[M + Na] + : 339.0997. Found: 339.0986.

[0436] Application Example 10:

[0437] In a protective atmosphere, compound 5, compound 15, ligand, additive 1, additive 2 are reacted in a solvent in the presence of a palladium catalyst to give a compound represented by compound 16;

[0438] wherein compound 15 is compound 16 is

[0439] The specific implementation steps are as follows:

[0440] To a degassed DMF (2 mL) mixture containing PdCl2(PPh3)2(7.0 mg, 10 mol%, 0.01 mmol), PPh3(2.6 mg, 10 mol%, 0.01 mmol) and Cul (1.9 mg, 1.0 eq, 0.1 mmol) was added compound 15 (42.1 mg, 1.5 eq, 0.15 mmol), compound 5 (47.1 mg, 0.1 mmol) and tetrabutylammonium fluoride solution (0.2 mL, 1 M in THF, 2.0 eq, 0.2 mmol) successively at room temperature under argon. The reaction turned dark immediately. After stirring at 100 °C for 12 h, the reaction was filtered through celite and the filtrate was washed successively with sodium chloride solution (15 mL), ethyl ether (15 mL x 3). The organic phase was combined and dried over anhydrous sodium sulfate before being concentrated under reduced pressure. The residue was separated and purified by column chromatography (petroleum ether / ethyl acetate = 20: 1) to give the product compound 16 (33.8 mg, yield 70%) as colorless oil.

[0441] 1 H NMR (400 MHz, CDC13) δ 7.59 (d, J = 7.6 Hz, 2H), 7.53 (d, J = 7.8 Hz, 2H), 7.44 - 7.33 (m, 4H), 7.20 (d, J = 7.9 Hz, 2H), 7.14 (d, J = 8.1 Hz, 2H), 6.96 (d, J = 8.4 Hz, 2H), 6.84 (s, 1H), 6.63 (d, J = 8.3 Hz, 2H), 3.68 (s, 3H). 13 C NMR (101 MHz, CDC13) δ 158.73, 142.76, 140.67, 140.23, 139.26, 139.24, 131.42, 131.02, 130.98, 129.87, 129.27, 128.97, 128.43, 127.56, 127.52, 127.09, 121.39, 113.66, 55.30. HRMS (EI) calcd. For C 27 H 21 BrO[M] + : 440.0776. Found: 440.0775.

[0442] The present application also provides the trans-1-boronyl-2-silyl olefins generated in the above Examples 1-40 as important synthetic building blocks, which can be converted into drug molecules (intermediates) and functional materials through stepwise conversion of the boronyl and silyl fragments, and the specific applications are as follows:

[0443] Application Example 11:

[0444] Step (1-1): Compound C-17, compound 18, additive under the action of rhodium catalyst, in the solvent, to obtain the compound shown in compound 19;

[0445] Step (1-2): Compound 19, compound 20, ligand, additive 1, additive 2 under the action of palladium catalyst, in the solvent, to obtain the compound shown in compound 21, compound 21 is antitumor drug CC-5079;

[0446] Compound C-17 is Compound 18 is Compound 19 is Compound 20 is Compound 21 is

[0447] The specific implementation steps are as follows:

[0448] Step (1-1): Compound C-17 (0.48 mmol, 1.2 equivalents), compound 18 (NCTS, 109 mg, 0.4 mmol, 1.0 equivalent), potassium carbonate (66.4 mg, 0.48 mmol, 1.2 equivalent) and bis(μ-hydroxy)bis(1,5-cyclooctadiene)dirhodium ([RhOH(cod)]2, 9.2 mg, 0.02 mmol, 10 mol% Rh) were added to a pressure tube under nitrogen protection. After adding degassed dioxane (4.0 mL), the mixture was stirred at 80°C for 4 hours. The reaction solution was filtered through a short column of silica gel (eluted with ethyl acetate), and the filtrate was concentrated by rotary evaporator, and then separated and purified by silica gel column chromatography (ethyl acetate / petroleum ether = 1:20) to obtain the corresponding product compound 19 (130 mg, yield 87%).

[0449] 1 H NMR (400 MHz, CDCl3) δ 8.88 (dd, J = 4.0, 1.9 Hz, 1H), 8.14 (dt, J = 8.2, 1.6 Hz, 1H), 7.88 (dd, J = 7.4, 1.4 Hz, 2H), 7.54 (td, J = 7.4, 1.3 Hz, 1H), 7.39 (ddd, J = 8.2, 4.2, 1.3 Hz, 1H), 6.80 (d, J = 1.5 Hz, 2H), 6.59 (s, 1H), 5.85 (d, J = 1.3 Hz, 1H), 3.83 (s, 3H), 3.58 (s, 3H), 0.58 (s, 6H). 13C NMR (101 MHz, CDC13) δ 170.51, 152.18, 149.45, 148.82, 148.45, 137.40, 136.97, 136.20, 132.77, 130.29, 127.80, 126.21, 121.23, 119.74, 117.42, 110.98, 110.47, 106.21, 55.81, 55.58, -1.75. HRMS (ESI) calcd. For C 22 H 22 N2O2Si[M+H] + : 375.2280. Found: 375.2267.

[0450] Step (1-2): To a degassed DMF (2 mL) mixture containing PdCl2(PPh3)2(7.0 mg, 5 mol%, 0.01 mmol), PPh3(5.2 mg, 10 mol%, 0.02 mmol) and Cul (3.8 mg, 1.0 eq, 0.2 mmol) was added compound 20 (3,5-di-OMeC6H3I, 79.2 mg, 1.5 eq, 0.3 mmol), compound 19 (74.8 mg, 0.2 mmol) and tetrabutylammonium fluoride solution (0.2 mL, 1 M in THF, 1.0 eq, 0.2 mmol) successively at room temperature under argon atmosphere. The reaction turned dark immediately. After stirring at 150 °C for 12 h, the reaction was filtered through a pad of celite, and the filtrate was washed with sodium chloride solution (15 mL), ethyl ether (15 mL x 3) successively. The organic phase was combined and dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was separated and purified by column chromatography (petroleum ether / ethyl acetate = 20: 1) to give the product compound 21 (35.7 mg, yield 55%) as colorless oil.

[0451] 1 H NMR (400 MHz, CDC13) δ 7.08 - 7.00 (m, 2H), 6.91 (d, J = 8.3 Hz, 1H), 6.53 (t, J = 2.3 Hz, 1H), 6.43 (d, J = 2.3 Hz, 2H), 5.60 (s, 1H), 3.90 (d, J = 24.9 Hz, 7H), 3.77 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 162.90, 160.85, 150.81, 148.74, 141.55, 129.37, 123.41, 118.44, 112.79, 110.87, 107.16, 102.22, 93.93, 56.24, 56.09, 55.64. HRMS (ESI) calcd. For C19 H 19 NNaO4[M+Na] + :348.1212.Found:348.1203.

[0452] Application Example 12:

[0453] Step (2-1): Compound C-22, compound 23, additive under the action of palladium catalyst, in the solvent, to obtain the compound shown in compound 24;

[0454] Step (2-2): Compound 24, compound 25, ligand, additive 1, additive 2 under the action of palladium catalyst, in the solvent, to obtain the compound shown in compound 26, compound 26 is a key intermediate for synthesizing TRPV1 antagonist;

[0455] Among them, compound C-22 is Compound 23 is Compound 24 is Compound 25 is Compound 26 is

[0456] The specific implementation steps are as follows:

[0457] Step (2-1): Compound C-22 (189.3 mg, 0.4 mmol), compound 23 (108.5 mg, 0.48 mmol) and dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium(PdCl2(dppf), 29.2 mg, 0.04 mmol) were added to a dry pressure tube and dissolved in anhydrous tetrahydrofuran (3 mL). Potassium hydroxide (67.2 mg, 1.2 mmol) and water (1 mL) were added to the mixture at room temperature. After sealing the reaction tube, it was heated to 80°C and stirred for 24 hours. After the reaction solution was quenched with water (2 mL), it was extracted with ethyl acetate (10 mL x 3). The combined organic phase was dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation under reduced pressure. The residue was separated and purified by silica gel column chromatography (n-hexane: ethyl acetate = 10:1) to obtain compound compound 24 (124.6 mg, yield 70%) as a colorless oil.

[0458] 1H NMR (400 MHz, CDC13) δ 8.86 (dd, J = 4.2, 1.8 Hz, 1H), 8.11 (dd, J = 8.3, 1.9 Hz, 1H), 8.06 (dd, J = 6.7, 1.5 Hz, 1H), 7.86 (dd, J = 8.1, 1.5 Hz, 1H), 7.77 (dd, J = 15.0, 11.9 Hz, 1H), 7.59 (dd, J = 8.2, 6.7 Hz, 1H), 7.35 (dd, J = 8.2, 4.2 Hz, 1H), 7.29 - 7.20 (m, 2H), 6.86 - 6.78 (m, 2H), 6.72 (dd, J = 11.9, 0.8 Hz, 1H), 5.75 (dd, J = 15.0, 0.8 Hz, 1H), 4.54 (hept, J = 6.1 Hz, 1H), 4.12 (q, J = 7.1 Hz, 2H), 1.34 (d, J = 6.1 Hz, 6H), 1.24 (t, J = 7.1 Hz, 3H), 0.60 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 167.19, 156.84, 152.11, 148.96, 143.93, 140.27, 139.85, 138.76, 136.45, 136.13, 129.72, 128.70, 127.82, 126.41, 122.05, 120.99, 115.33, 69.97, 60.15, 22.24, 14.42, 0.65. HRMS (ESI) calcd. For C 27 H 32 NO3Si[M + H] + : 446.2151. Found: 446.2151.

[0459] Step (2-2): To a degassed DMF (2 mL) mixture containing PdCl2(PPh3)2(7.0 mg, 5 mol%, 0.01 mmol), PPh3(5.2 mg, 10 mol%, 0.02 mmol) and Cul (3.8 mg, 1.0 eq, 0.2 mmol) under argon, compound 25 (4-CF3C6H4I, 79.2 mg, 1.5 eq, 0.3 mmol), compound 24 (89.0 mg, 0.2 mmol) and a solution of tetrabutylammonium fluoride (0.2 mL, 1 M in THF, 1.0 eq, 0.2 mmol) were added sequentially at room temperature. The reaction turned dark immediately. After stirring at 150 °C for 12 h, the reaction was filtered through a pad of celite, which was washed with a sodium chloride solution (15 mL), and then with diethyl ether (15 mL x 3). The organic phase was combined and dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The residue was separated and purified by column chromatography (petroleum ether / ethyl acetate = 10:1) to give the product compound 26 (52.5 mg, yield 65%) as a colorless oil.

[0460] 1 H NMR (400 MHz, CDCb) d 7.70 (d, J = 7.8 Hz, 2H), 7.37 (d, J = 7.8 Hz, 2H), 7.29 (d, J = 2.4 Hz, 1H), 7.21 (dd, J = 8.8, 2.6 Hz, 2H), 6.89 - 6.78 (m, 3H), 6.06 (dd, J = 15.3, 2.4 Hz, 1H), 4.59 (p, J = 6.6 Hz, 1H), 4.25 - 4.14 (m, 2H), 1.37 (dd, J = 6.3, 2.3 Hz, 6H), 1.30 - 1.26 (m, 3H). 13 C NMR (101 MHz, CDCb) d 167.12, 158.44, 149.24, 145.55, 142.00, 131.91, 130.31 (q, 2 J C-F = 32.6 Hz), 129.88, 128.66, 126.49, 125.28 (q, 3 J C-F = 3.3 Hz), 124.16 (q, 1 J C-F = 273.2 Hz), 123.17, 115.59, 69.97, 60.40, 22.13, 14.35. 19 F NMR (376 MHz, CDCb) d -62.59. HRMS (ESI) calcd. For C 23 H 24 F3O3 [M + H] +:405.1678.Found:406.1675.

[0461] Example 13:

[0462] Step (3-1): Compound C-27, compound 4, additive were reacted in the presence of a palladium catalyst in a solvent to obtain a compound represented by compound 28; Step (3-2): Compound 28, N-chlorosuccinimide, silver fluoride were reacted in a solvent to obtain a compound represented by compound 29, which is a long-acting non-steroidal estrogen and also an orally effective estrogen receptor modulator;

[0463] wherein compound C-27 is compound 4 is compound 28 is compound 29 is

[0464] The specific implementation steps are as follows:

[0465] Step (3-1): Compound C-27 (178 mg, 0.4 mmol), compound 4 (187.2 mg, 0.8 mmol) and dichloro(1,1'-bis(diphenylphosphino)ferrocene)palladium (PdCl2(dppf), 29.2 mg, 0.04 mmol) were added to a dry pressure tube and dissolved in anhydrous tetrahydrofuran (3 mL). Potassium hydroxide (67.2 mg, 1.2 mmol) and water (1 mL) were added to the mixture at room temperature. After sealing the reaction tube, it was heated to 80°C and stirred for 24 hours. After the reaction solution was quenched with water (2 mL), it was extracted with ethyl acetate (10 mL x 3). The combined organic phase was dried over anhydrous magnesium sulfate and the solvent was removed by rotary evaporation under reduced pressure. The residue was separated and purified by silica gel column chromatography (n-hexane: ethyl acetate = 20:1) to obtain compound 28 (176.3 mg, yield 83%) as a white solid.

[0466] 1H NMR (400 MHz, CDC13) δ 8.95 (dd, J = 4.2, 1.8 Hz, 1H), 8.07 (dd, J = 8.3, 1.9 Hz, 1H), 7.68 (dd, J = 8.1, 1.5 Hz, 1H), 7.41 - 7.34 (m, 2H), 7.30 (dd, J = 8.0, 6.7 Hz, 1H), 7.21 - 7.13 (m, 2H), 6.85 - 6.72 (m, 4H), 6.60 - 6.54 (m, 2H), 6.54 - 6.46 (m, 2H), 6.35 - 6.27 (m, 2H), 3.78 (s, 3H), 3.69 (s, 3H), 3.64 (s, 3H), 0.29 (s, 6H). 13 CNMR (101 MHz, CDC13) δ 158.08, 157.35, 157.06, 152.00, 151.74, 148.48, 142.61, 141.75, 137.39, 136.86, 136.45, 135.79, 135.41, 131.04, 130.97, 130.45, 128.27, 127.47, 125.95, 120.57, 112.88, 112.56, 112.42, 55.18, 55.15, 55.04. HRMS (ESI) calcd. For C 34 H 33 NNaO3Si[M+Na] + : 554.2127. Found: 554.2116.

[0467] Step (3-2): To acetonitrile (2 mL) was added compound 28 (106.2 mg, 0.2 mmol), N-chlorosuccinimide (NCS, 53.4 mg, 0.4 mmol, 2.0 eq) and silver fluoride (AgF, 101.5 mg, 0.8 mmol, 4.0 eq) at room temperature under argon protection. The reaction mixture was stirred at 40 °C for 24 h under nitrogen protection. Quench with saturated aqueous sodium sulfite solution and continue stirring for 1 h. Extracted with ethyl acetate (10 mL x 3), dried the combined organic phase over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The crude product was isolated and purified by column chromatography (petroleum ether / ethyl acetate = 10:1) to give the product compound 29 (58.5 mg, yield 77%) as colorless oil.

[0468] 1H NMR (400 MHz, CDCI3) δ 7.24 - 7.17 (m, 4H), 6.82 (ddt, J = 8.4, 6.6, 2.3 Hz, 4H), 6.69 - 6.62 (m, 2H), 6.57 (dt, J = 8.8, 2.2 Hz, 2H), 3.77 (d, J = 1.4 Hz, 3H), 3.71 (d, J = 1.3 Hz, 3H), 3.67 (d, J = 1.4 Hz, 3H). 13 CNMR (101 MHz, CDCI3) δ 159.08, 158.89, 158.50, 138.62, 134.96, 134.18, 132.36, 132.06, 131.52, 131.41, 128.50, 113.52, 113.46, 113.44, 55.35, 55.25. HRMS (ESI) calcd. For C 23 H 22 ClO3[M+H] + : 381.1257. Found: 381.1248.

[0469] Example 14:

[0470] Step (4-1): compound C-30, compound 31, additive are reacted in the presence of a palladium catalyst in a solvent to obtain a compound represented by compound 32;

[0471] Step (4-2): compound 32, tetrabutylammonium fluoride are reacted in a solvent to obtain a compound represented by compound 33, and compound 33 is a photochromic material;

[0472] wherein compound C-30 is compound 31 is compound 32 is compound 33 is

[0473] The specific implementation steps are as follows:

[0474] Compound C-30 (168.4 mg, 0.4 mmol), compound 31 (176.8 mg, 0.8 mmol) and dichloro(l,l'-bis(diphenylphosphino)ferrocene)palladium (PdCl2(dppf), 29.2 mg, 0.04 mmol) were added into a dry pressure tube under argon protection, and dissolved in anhydrous tetrahydrofuran (3 mL). Potassium hydroxide (67.2 mg, 1.2 mmol) and water (1 mL) were added into the mixture at room temperature. After sealing the reaction tube, the temperature was raised to 80 °C and the reaction was stirred for 24 h. The reaction solution was quenched with water (2 mL) and extracted with ethyl acetate (10 mL x 3). The organic phase was combined and dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation under reduced pressure. The residue was separated and purified by silica gel column chromatography (n-hexane: ethyl acetate = 20: 1) to obtain compound compound 32 (152.6 mg, yield 79%) as a colorless oil.

[0475] 1 H NMR (400 MHz, CDC13) δ 8.98 (dt, J = 4.0, 2.0 Hz, 1H), 8.10 (d, J = 8.0 Hz, 1H), 7.73 (d, J = 8.1 Hz, 1H), 7.45 - 7.29 (m, 3H), 7.08 - 7.02 (m, 1H), 7.01 - 6.89 (m, 2H), 6.87 - 6.80 (m, 1H), 6.79 - 6.55 (m, 5H), 6.54 - 6.44 (m, 2H), 0.33 (s, 6H). 13 C NMR (101 MHz, CDC13) δ 162.83 (d, J = 52.4 Hz), 160.38 (d, J = 52.7 Hz), 153.75, 151.97, 148.69, 145.42, 140.81, 139.51 (d, J = 3.5 Hz), 139.28 (d, J = 3.3 Hz), 137.56, 135.98, 135.59, 130.99 (d, J = 8.0 Hz), 130.71 (d, J = 8.1 Hz), 128.78, 127.56, 126.47, 126.32, 126.13, 124.19, 120.84, 114.36 (d, J = 21.2 Hz), 114.06 (d, J = 21.5 Hz), 0.12. 19 F NMR (376 MHz, CDC13) δ -115.75, -115.80. HRMS (ESI) calcd. For C 29 H 24 F2NSSi [M+H] + : 484.1367. Found: 484.1360.

[0476] To an 8 mL reaction vial was added compound 32 (96.6 mg, 0.2 mmol), tetrahydrofuran (2 mL) and tetrabutylammonium fluoride solution (0.4 mL, 1.0 M in THF). After the reaction mixture was stirred at room temperature for 12 h, it was concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel (eluent: n-hexane / ethyl acetate = 30: 1) to give the target product compound 33 (54.8 mg, yield 92%) as a colorless oil. 1 H NMR (400 MHz, CDC13) δ 7.28 (dd, J = 5.1, 1.9 Hz, 1H), 7.25 (d, J = 2.2 Hz, 2H), 7.22 (d, J = 6.7 Hz, 2H), 7.20 - 7.14 (m, 2H), 7.07 (dt, J = 5.1, 1.0 Hz, 1H), 7.02 - 6.97 (m, 2H), 6.96 - 6.92 (m, 1H), 6.89 (dd, J = 5.1, 3.6 Hz, 1H). 13 C NMR (101 MHz, CDC13) δ 164.00 (d, J = 59.8 Hz), 161.54 (d, J = 60.4 Hz), 141.09, 138.01 (d, J = 3.5 Hz), 137.81, 135.20 (d, J = 3.5 Hz), 132.26 (d, J = 8.2 Hz), 129.30, 128.49 (d, J = 8.1 Hz), 126.45, 121.37, 121.35, 116.63 (d, J = 21.4 Hz), 115.39 (d, J = 21.4 Hz). 19 F NMR (376 MHz, CDC13) δ -113.55, -114.75. HRMS (EI) calcd for C 18 H 12 F2S[M] + : 298.0628. Found: 298.0622.

[0477] The above examples are merely for illustration and are not intended to limit the embodiments. Based on the above description, those skilled in the art can make other variations or changes in different forms. Here, all the embodiments cannot be exhaustively listed. The obvious variations or changes derived therefrom are still within the protection scope of the present application.

Claims

1. A silicon boron reagent characterized in that, has a structure as shown in formula A:

2. A process for the preparation of a silicon-boron reagent as claimed in claim 1, characterized in that, The method comprises the following steps: Step (I): under a protective atmosphere, 8-bromoquinoline, n-butyllithium, Me2HSiCl are used as raw materials to react in an organic solvent to generate a compound shown in formula B; wherein the structural formula of formula B is Step (II): under a protective atmosphere, the compound shown in formula B and B2Pin2 are used as raw materials to react in an organic solvent under the action of a platinum catalyst to generate a silicon-boron reagent shown in formula A.

3. The method of claim 2, wherein, in step (I), the molar ratio of 8-bromoquinoline, n-butyllithium, Me2HSiCl is 1:(0.5-2.0):(0.5-2.0); and / or, the concentration of 8-bromoquinoline in the solvent is (0.1-2) mol / L; and / or, the reaction temperature is -78℃ to room temperature; and / or, the reaction time is 1-48 hours; and / or, the organic solvent is at least one of tetrahydrofuran, 2-methyltetrahydrofuran, toluene, anhydrous diethyl ether, 1,2-dichloroethane, n-hexane, cyclohexane, n-heptane, n-octane, dioxane; and / or, in step (II), the platinum catalyst is at least one of tetraphenylphosphine platinum, dichlorobis(triethylphosphine) platinum, dichloro(vinyl) platinum, (1,5-cyclooctadiene) dibromide platinum, 2,2'-bipyridine dichloro platinum, bis(acetylacetone) platinum, platinum dichloride, bis(acetonitrile) dichloro platinum, tris(dibenzalacetone) platinum, dichlorobis(triphenylphosphine) platinum, alkenyl bis(triphenylphosphine) platinum, [1,1'-bis(diphenylphosphino) ferrocene] dichloro platinum; and / or, the molar ratio of formula B, platinum catalyst, B2Pin2 is 1:(0.01-0.2):(1.0-5.0); and / or, the concentration of formula B in the solvent is 0.1-1.0 mol / L; and / or, the reaction temperature is 50-150℃; and / or, the reaction time is 12-48 hours; and / or, the organic solvent is at least one of cyclohexane, tetrahydrofuran, 2-methyltetrahydrofuran, toluene, anhydrous diethyl ether, 1,2-dichloroethane, n-hexane, n-heptane, n-octane, dioxane, alcohol, dichloromethane, carbon tetrachloride.

4. A method for preparing trans-1-bora-2-silene using the silicon boron reagent of claim 1, characterized in that, The method comprises the following steps: under the action of a catalyst, the silicon-boron reagent and an alkyne are subjected to an addition reaction in an organic solvent to obtain a trans-1-boron-2-silene compound shown in formula C; wherein the silicon-boron reagent is the silicon-boron reagent of claim 1; The structure of the alkyne is wherein R is heteroaryl, naphthyl, wherein R1 is aryl, C1-C10 alkyl, C1-C10 alkoxy, C1-C10 ester, cyano, C1-C10 haloalkyl, C1-C10 aldehyde, nitro, pinacol borate, trimethylsilyl (TMS), C1-C10 alkynyl, and n is an integer from 1 to 3; The structure of the compound of formula C is wherein 8-Qu represents 8-quinolinyl of the compound of formula A, i.e. R corresponds to R in the alkyne compound.

5. The method of claim 4, wherein, in the alkyne, R is in which R1is phenyl, C1-C5alkyl, C1-C5alkoxy, C1-C5ester, cyano, C1-C5haloalkyl, C1-C5aldehyde, nitro, pinacol borate, trimethylsilyl, C1-C5alkynyl, n is an integer from 1 to 2; halogen is F, Br, Cl; R is heteroaryl, then the heteroaryl group is the alkyne is selected from at least one of the following compounds: the catalyst is at least one of Pd(OAc)2, Pd(acac)2, Pd(PPh3)4, Pd(dba)2, Pd2(dba)3, Pd(dppf)Cl2, Pd(cod)Cl2, Pd(MeCN)2Cl2, NiCl2DME, Ni(cod)2, Ni(OTf)2; and / or, The organic solvent is at least one of cyclohexane, n-hexane, n-heptane, dichloromethane, tetrahydrofuran, methyl tert-butyl ether, methyl cyclopentyl ether, acetonitrile, N,N-dimethylformamide, toluene, chlorobenzene, chloroform, 1,2-dichloroethane; and / or, The molar ratio of the silicon-boron reagent, olefin, catalyst is 1:(0.5-5):(0.01-0.5); and / or, The concentration of the silicon-boron reagent in the organic solvent is (0.05-1.0) mol / L; and / or, The addition reaction temperature is 50-120°C; and / or, The addition reaction time is 12-48 hours.

6. A trans-1-bora-2-silene, characterized in that, The compound C-1 has a structural formula as shown in formula C: The structure of the compound of formula C is wherein 8-Qu represents an 8-quinolinyl group of the compound of formula A, i.e. R corresponds to R in the alkyne compound according to any one of claims 4-5; Preferably, the formula C is at least one selected from the following compounds:

7. The use of the trans-1-boryl-2-silyl olefin of claim 6 as a synthetic building block in organic synthesis, characterized in that, The use of the compound C-1 in the structure of formula C as a synthetic building block in organic synthesis; the structural formula of the compound C-1 is: Preferably, The application 1 is that, under a protective atmosphere, the compound C-1, the compound 2, the ligand, the additive are reacted in a solvent under the action of a palladium catalyst to obtain a compound shown in the compound 3; wherein compound 2 is Compound 3 is Preferably, in the application 1, The palladium catalyst is at least one of Pd(acac)2, Pd(PPh3)4, Pd(dba)2, Pd2(dba)3, Pd(OAc)2; and / or, The ligand is at least one of P t Bu)2Me, PMe3, P t Bu)3, P t Bu)Me2; and / or, The additive is at least one of NaOH, KOH, LiOH, NaCO3, K2CO3; and / or, The molar ratio of the compound C-1, the compound 2, the palladium catalyst, the ligand, the additive is 1:(0.5-2.0):(0.01-0.5):(0.02-1.0):(1.0-5.0); and / or, The concentration of the compound C-1 in the solvent is (0.05-1.0) mol / L; and / or, The reaction temperature is room temperature to 100°C; and / or, The reaction time is 12-48 hours; Or, The application 3 is that the compound C-1, copper acetate are reacted in a solvent to obtain a compound shown in formula 7; wherein formula 7 is Preferably, in the application 3, The molar ratio of the compound C-1, copper acetate is 1:(0.2-2.0); and / or, The solvent is at least one of anhydrous ethanol, N,N-dimethylformamide, toluene, anhydrous methanol, N,N-dimethylacetamide, dichloromethane; and / or, The concentration of the compound C-1 in the solvent is (0.05-0.2) mol / L; and / or, The reaction temperature is room temperature to 100°C; and / or, The reaction time is 2-12 hours; Or, The application 4 is that, under a protective atmosphere, the compound C-1, copper bromide are reacted in a solvent to obtain a compound shown in formula 8; wherein, formula 8 is Preferably, in the application 4, The molar ratio of the compound C-1, copper bromide is 1:(1.0-5.0); and / or, The solvent is at least one of anhydrous methanol, anhydrous ethanol, water, tetrahydrofuran, acetonitrile, isopropanol; and / or, The concentration of the compound C-1 in the solvent is 0.01-0.5 mol / L; and / or, The reaction temperature is room temperature to 120°C; and / or, The reaction time is 2-12 hours; Alternatively, The application 5 is: under a protective atmosphere, the compound C-1, sodium azide, reacts in a solvent under the action of a copper catalyst to obtain a compound shown in formula 9; wherein formula 9 is Preferably, in the application 5, The copper catalyst is at least one of copper sulfate, copper acetate, cuprous iodide, cuprous bromide; and / or, The solvent is at least one of anhydrous methanol, anhydrous ethanol, isopropanol, toluene, tetrahydrofuran, anhydrous diethyl ether; and / or, The molar ratio of the compound C-1, sodium azide, copper catalyst is 1:(0.5-2.0):(0.1-1.0); and / or, The concentration of the compound C-1 in the solvent is 0.01-1.0 mol / L; and / or, The reaction temperature is room temperature to 60°C; and / or, The reaction time is 2-12 hours; Alternatively, The application 6 is: under a protective atmosphere, the compound C-1, compound 10, reacts in a solvent under the action of a rhodium catalyst to obtain a compound shown in compound 11; wherein compound 10 is Compound 11 is Preferably, in the application 6, The rhodium catalyst is at least one of chloro(ethylene)rhodium dimer, dimeric hydroxy(1,5-cyclooctadiene)rhodium, bis(acetylacetone)rhodium, (1,5-cyclooctadiene)acetylacetone rhodium, chloro(phenyl)rhodium; and / or, The solvent is at least one of anhydrous methanol, anhydrous ethanol, water, tetrahydrofuran, toluene, dichloromethane; and / or, The molar ratio of the compound C-1, compound 10, rhodium catalyst is 1:(0.5-2.0):(0.01-0.2); and / or, The concentration of the compound C-1 in the solvent is 0.01-0.5 mol / L; and / or, The reaction temperature is 50-130°C; and / or, The reaction time is 6-24 hours.

8. The application of the trans-1-boryl-2-silylalkene as a synthetic building block in organic synthesis according to claim 6, characterized in that, The compound C-1 in the structure of formula C is used as a synthetic building block in organic synthesis; the structural formula of compound C-1 is Preferably, The application 2 is: step A: under a protective atmosphere, the compound C-1, compound 4, additive, reacts in a solvent under the action of a palladium catalyst to obtain a compound shown in compound 5 or compound 6; wherein compound 4 is compound 5 is compound 6 is Preferably, in step A of the application 2, The palladium catalyst is at least one of bis-tri-tert-butylphosphine palladium, tetra-triphenylphosphine palladium, palladium acetate, palladium triflate, tris(dibenzylideneacetone)dipalladium, palladium acetylacetone, DPPF dichloropalladium; and / or, The additive is at least one of sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, disodium hydrogen phosphate; and / or, The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane; and / or, The molar ratio of the compound C-1, compound 4, palladium catalyst, additive is 1:(1.0-2.0):(0.05-0.2):(1.0-3.0); and / or, The concentration of the compound C-1 in the solvent is 0.05-0.2 mol / L; and / or, The reaction temperature is room temperature to 100°C; and / or, The reaction time is 12-48 hours; Further preferably, Step B-1: compound 5, tetrabutylammonium fluoride, react in a solvent to obtain a compound represented by compound 12; wherein compound 12 is Preferably, in the step B-1 of the application 2, The molar ratio of the compound 5, tetrabutylammonium fluoride is 1:(1.0-3.0); and / or, The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane; and / or, The concentration of the compound 5 in the solvent is 0.05-0.2 mol / L; and / or, The reaction temperature is room temperature to 60°C; and / or, The reaction time is 2-24 hours; Or, Step B-2: under a protective atmosphere, compound 5, 18-crown-6-ether, potassium tert-butoxide, heavy water, react in a solvent to obtain a compound represented by compound 13; wherein compound 13 is Preferably, in the step B-2 of the application 2, The molar ratio of the compound 5, 18-crown-6-ether, potassium tert-butoxide, heavy water is 1:(1.0-3.0):(1.0-3.0):(2.0-10.0); and / or, The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane; and / or, The concentration of the compound 5 in the solvent is 0.05-0.2 mol / L; and / or, The reaction temperature is room temperature to 100°C; and / or, The reaction time is 2-24 hours; Or, Step B-3: under a protective atmosphere, compound 5, m-chloroperoxybenzoic acid, sodium bicarbonate, react in a solvent to obtain a compound represented by compound 14; wherein compound 14 is Preferably, in the step B-3 of the application 2, The molar ratio of the compound 5, m-chloroperoxybenzoic acid, sodium bicarbonate is 1:(1.0-3.0):(1.0-3.0); and / or, The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane; and / or, The concentration of the compound 5 in the solvent is 0.05-0.2 mol / L; and / or, The reaction temperature is room temperature to 60°C; and / or, The reaction time is 2-24 hours; Or, Step B-4: under a protective atmosphere, compound 5, compound 15, ligand, additive 1, additive 2, react in a solvent under the action of a palladium catalyst to obtain a compound represented by compound 16; wherein compound 15 is Compound 16 is Preferably, in the step B-4 of the application 2, The palladium catalyst is at least one of dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, palladium di-tert-butylphosphine; and / or, the ligand is at least one of triphenylphosphine, trifuranylphosphine, trithienylphosphine, tricyclohexylphosphine; and / or, the additive 1 is at least one of cuprous iodide, cuprous bromide, cuprous chloride; and / or, the additive 2 is at least one of tetrabutylammonium fluoride, tetramethylammonium fluoride, potassium fluoride; and / or, the solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide; and / or, the molar ratio of the compound 5, the compound 15, the palladium catalyst, the ligand, the additive 1, the additive 2 is 1:(1.0-3.0):(0.02-0.2):(0.04-0.4):(0.5-3.0):(0.5-3.0); and / or, the concentration of the compound 5 in the solvent is 0.02-0.2 mol / L; and / or, the reaction temperature is 60-150°C; and / or, the reaction time is 12-48 hours.

9. Use of the trans-1-boryl-2-silylalkene in claim 6 as a synthetic building block in organic synthesis, characterized in that, the use of the compound C-17 in the structure of formula C as a synthetic building block in organic synthesis 7 comprises the following steps: Step (1-1): under a protective atmosphere, the compound C-17, the compound 18, the additive are reacted in a solvent under the action of a rhodium catalyst to obtain a compound represented by the compound 19; Step (1-2): under a protective atmosphere, the compound 19, the compound 20, the ligand, the additive 1, the additive 2 are reacted in a solvent under the action of a palladium catalyst to obtain a compound represented by the compound 21; wherein compound C-17 is Compound 18 is Compound 19 is Compound 20 is Compound 21 is Preferably, in step (1-1) of the use 7, the rhodium catalyst is at least one of chloro rhodium dicyclocotane dimer, dimerized hydroxyl (1,5-cyclooctadiene) rhodium, acetylacetone bis (ethylene) rhodium, (1,5-cyclooctadiene) acetylacetone rhodium, triphenylphosphine rhodium chloride; and / or, the additive is at least one of sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate; and / or, the solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, toluene, dioxane, methyl tert-butyl ether; and / or, the molar ratio of the compound C-17, the compound 18, the rhodium catalyst, the additive is (1.0-2.0):1:(0.01-0.1):(1.0-2.0); and / or, the concentration of the compound C-17 in the solvent is 0.02-0.5 mol / L; and / or, the reaction temperature is room temperature to 120°C; and / or, the reaction time is 2-12 hours; in step (1-2) of the use 7, the palladium catalyst is at least one of dichloropalladium trisphenylphosphine, tetrakis palladium triphenylphosphine, palladium di-tert-butylphosphine; and / or, the ligand is at least one of triphenylphosphine, trifuranylphosphine, trithienylphosphine, tricyclohexylphosphine; and / or, the additive 1 is at least one of cuprous iodide, cuprous bromide, cuprous chloride; and / or, The additive 2 is at least one of tetrabutylammonium fluoride, tetramethylammonium fluoride, potassium fluoride; and / or, The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide; and / or, The molar ratio of the compound 19, the compound 20, the palladium catalyst, the ligand, the additive 1, the additive 2 is 1:(1.0-3.0):(0.01-0.2):(0.02-0.4):(0.5-2.0):(0.5-2.0); and / or, The concentration of the compound 19 in the solvent is (0.02-0.2) mol / L; and / or, The reaction temperature is 100-180°C; and / or, The reaction time is 6-24 hours; Or, The application 8 of the compound C-22 in the structure of formula C as a synthetic building block in organic synthesis comprises the following steps: Step (2-1): under a protective atmosphere, the compound C-22, the compound 23, the additive are reacted in the solvent under the action of the palladium catalyst to obtain the compound represented by the compound 24; Step (2-2): under a protective atmosphere, the compound 24, the compound 25, the ligand, the additive 1, the additive 2 are reacted in the solvent under the action of the palladium catalyst to obtain the compound represented by the compound 26; wherein compound C-22 is Compound 23 is Compound 24 is Compound 25 is Compound 26 is Preferably, in the step (2-1) of the application 8, The palladium catalyst is at least one of di-tri-tert-butylphosphine palladium, tetra-triphenylphosphine palladium, palladium acetate, palladium triflate, tris(dibenzylideneacetone)dipalladium, palladium acetylacetone, DPPF palladium dichloride; and / or, The additive is at least one of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate; and / or, The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, water, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide; and / or, The molar ratio of the compound C-22, the compound 23, the palladium catalyst, the additive is 1:(0.5-2.0):(0.05-0.5):(1.0-3.0); and / or, The concentration of the compound C-22 in the solvent is (0.05-0.2) mol / L; and / or, The reaction temperature is room temperature to 120°C; and / or, The reaction time is 12-48 hours; In the step (2-2) of the application 8, The palladium catalyst is at least one of triphenylphosphine palladium dichloride, tetraphenylphosphine palladium, di-tert-butylphosphine palladium; and / or, The ligand is at least one of triphenylphosphine, tri-furfuryl phosphine, tri-thienyl phosphine, tricyclohexylphosphine; and / or, The additive 1 is at least one of cuprous iodide, cuprous bromide, cuprous chloride; and / or, The additive 2 is at least one of tetrabutylammonium fluoride, tetramethylammonium fluoride, potassium fluoride; and / or, The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide; and / or, The molar ratio of the compound 24, the compound 25, the palladium catalyst, the ligand, the additive 1, the additive 2 is 1:(0.5-3.0):(0.02-0.5):(0.04-1.0):(0.5-2.0):(0.5-2.0); and / or, The concentration of the compound 24 in the solvent is (0.05-0.5) mol / L; and / or, The reaction temperature is 100-180℃; and / or, The reaction time is 6-24 hours.

10. The use of the trans-1-boryl-2-silylalkene in claim 6 as a synthetic building block in organic synthesis, characterized in that, The use of the compound C-27 in the structure of formula C as a synthetic building block in organic synthesis 9 comprises the following steps: Step (3-1): under a protective atmosphere, the compound C-27, the compound 4, the additive are reacted in the solvent under the action of the palladium catalyst to obtain the compound represented by the compound 28; Step (3-2): under a protective atmosphere, the compound 28, N-chlorosuccinimide, silver fluoride are reacted in the solvent to obtain the compound represented by the compound 29; wherein compound C-27 is Compound 4 is Compound 28 is Compound 29 is Preferably, in step (3-1) of application 9, The palladium catalyst is at least one of di-tri-tert-butylphosphine palladium, tetra-triphenylphosphine palladium, palladium acetate, palladium triflate, tris(dibenzylideneacetone)dipalladium, palladium acetylacetone, DPPF palladium dichloride; and / or, The additive is at least one of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate; and / or, The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide; and / or, The molar ratio of the compound C-27, the compound 4, the palladium catalyst, the additive is 1:(1.5-3.0):(0.05-0.2):(2.0-4.0); and / or, The concentration of the compound C-27 in the solvent is (0.05-0.5) mol / L; and / or, The reaction temperature is room temperature to 120℃; and / or, The reaction time is 12-48 hours; In step (3-2) of application 9, The molar ratio of the compound 28, N-chlorosuccinimide, silver fluoride is 1:(1.0-3.0):(1.0-5.0); and / or, The solvent is at least one of acetonitrile, tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide; and / or, The concentration of the compound 28 in the solvent is (0.05-0.5) mol / L; and / or, The reaction temperature is room temperature to 80℃; and / or, The reaction time is 12-48 hours; Or, The application of compound C-30 in structure of formula C as a synthetic building block in organic synthesis 10, comprising the following steps: Step (4-1): under a protective atmosphere, compound 30, compound 31, an additive, under the action of a palladium catalyst, in a solvent, to obtain a compound represented by compound 32; Step (4-2): compound 32, tetrabutylammonium fluoride, in a solvent, to obtain a compound represented by compound 33; wherein the compound C-30 is Compound 31 is Compound 32 is Compound 33 is In step (4-1), The palladium catalyst is at least one of di-tri-tert-butylphosphine palladium, tetra-triphenylphosphine palladium, palladium acetate, palladium triflate, tris(dibenzylideneacetone) dipalladium, palladium acetylacetone, DPPF dichloropalladium; and / or, The additive is at least one of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate; and / or, The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, water, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide; and / or, The molar ratio of compound C-30, compound 31, palladium catalyst, additive is 1:(1.5-3.0):(0.05-0.5):(1.0-4.0); and / or, The concentration of compound C-30 in the solvent is (0.05-0.5) mol / L; and / or, The reaction temperature is room temperature to 120°C; and / or, The reaction time is 12-48 hours; In step (4-2), The molar ratio of compound 32, tetrabutylammonium fluoride is 1:(1.0-5.0); and / or, The concentration of compound 32 in the solvent is (0.05-0.5) mol / L; and / or, The solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, toluene, anhydrous methanol, anhydrous ethanol, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide; and / or, The reaction temperature is room temperature to 60°C; and / or, The reaction time is 6-24 hours.

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