CN113880871B - Preparation method of saturated monoboron compound - Google Patents

Preparation method of saturated monoboron compound Download PDF

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CN113880871B
CN113880871B CN202011110322.3A CN202011110322A CN113880871B CN 113880871 B CN113880871 B CN 113880871B CN 202011110322 A CN202011110322 A CN 202011110322A CN 113880871 B CN113880871 B CN 113880871B
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CN113880871A (en
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吴立朋
李思达
崔鑫
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C07—ORGANIC CHEMISTRY
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    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07F17/00—Metallocenes
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Abstract

The invention relates to the technical field of organic synthesis, in particular to a preparation method of a saturated monoboron compound. The preparation method provided by the invention comprises the following steps: mixing an olefin compound, an alkali compound, a boron halide compound and an organic solvent, carrying out a boronation reaction, adding triethylamine and pinacol or adding triethylamine and 1,8-diaminonaphthalene, and carrying out an esterification reaction to obtain the saturated monoboron compound. The preparation method is simple to operate and low in cost, can selectively introduce boron into olefin sites under the condition of no metal catalysis, avoids the possibility of double bond directional isomerization in the traditional transition metal catalysis olefin hydroboration reaction, and prepares the saturated monoboron compound.

Description

Preparation method of saturated monoboron compound
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of a saturated monoboron compound.
Background
Organoboron compounds are widely used as important intermediates in synthetic chemistry in research fields such as material science and medical industry. Organic borates are compounds with a wide range of conversion and synthesis values due to their relative stability, high functional group compatibility and broad reactivity. In recent years, boron-containing compounds have gained increasing attention from chemists as a class of very useful synthetic intermediates and pharmaceutical precursor compounds.
Despite the great advances made in hydroboration of olefins, the conventional hydroboration reaction systems are also active for double bond isomerization of olefins, since they are catalyzed by metal hydrides generated in situ. Thus, regardless of the position of the double bond, the boron-containing moiety is typically added at the alpha-carbon or less hindered terminal position of the activated aryl or boryl unit. Thus, selective incorporation of boron into the internal olefin double bond at the original site also presents certain challenges.
Disclosure of Invention
The invention aims to provide a preparation method of a saturated monoboron compound, which is simple to operate and low in cost, and can selectively introduce boron into olefin sites under the condition of no metal catalysis and prepare the saturated monoboron compound.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a saturated monoboron compound, which comprises the following steps:
mixing an olefin compound, an alkali compound, a boron halide compound and an organic solvent, carrying out a boronization reaction, adding triethylamine and pinacol or adding triethylamine and 1,8-diaminonaphthalene, and carrying out an esterification reaction to obtain the saturated monoboron compound.
Preferably, the molar ratio of the olefin compound, the alkali compound and the boron halide compound is 1: (1-6): (1-6).
Preferably, the olefinic compound has a structure represented by formula 1 or formula 2:
Figure BDA0002728382220000011
wherein R is 1 Is aryl, aromatic heterocycle or alkyl, R 2 、R 3 And R 4 Independently aryl, alkyl or hydrogen.
Preferably, said R is 1 Beta-naphthalene, ferrocene, N-methylindole, phenyl, substituted phenyl or alkyl;
the substituent in the substituted phenyl is methyl, fluorine, chlorine, bromine, tertiary butyl, phenyl, trifluoromethyl, pentafluorophenyl or methylthio.
Preferably, the molar ratio of the olefin compound to the triethylamine is 1: 3;
the molar ratio of the olefin compound to the pinacol is 1: 1.5;
the molar ratio of the olefin compound to the 1,8-diaminonaphthalene is 1: 1.5.
Preferably, the alkali compound is diisopropylethylamine or isopropylamine.
Preferably, the boron halide compound is boron tribromide, boron trichloride or boron tribromide dimethylsulfide complex.
Preferably, the organic solvent is toluene, dichloromethane, 1, 2-dichloroethane or n-hexane.
Preferably, the temperature of the boronization reaction is 20-80 ℃, and the time of the boronization reaction is 1-24 hours.
Preferably, the boronation reaction is carried out in a protective atmosphere;
the protective atmosphere is nitrogen atmosphere or argon atmosphere.
The invention provides a preparation method of a saturated monoboron compound, which comprises the following steps: mixing an olefin compound, an alkali compound, a boron halide compound and an organic solvent, carrying out a boronation reaction, adding triethylamine and pinacol or adding triethylamine and 1,8-diaminonaphthalene, and carrying out an esterification reaction to obtain the saturated monoboron compound. The preparation process can selectively introduce boron into an olefin site under the condition of no metal catalysis, avoids the possibility of double bond directional isomerization in the traditional transition metal catalysis olefin hydroboration reaction, and prepares the saturated monoboron compound.
Compared with the prior art, the preparation method has the following advantages:
1. the method does not use any metal catalyst, avoids metal and ligand pollution, improves the atom economy of the reaction, and meets the requirement of green chemistry;
2. the raw materials are cheap and easy to obtain, and the production cost is low;
3. the reaction condition is mild, the operation is simple and convenient, and the method is suitable for industrial production;
4. the boric acid ester can be introduced in site selectivity, so that the possibility of producing isomers or single products by traditional transition metal catalysis is avoided.
5. The synthesized saturated borate compound has high conversion rate and good selectivity, and is beneficial to separation and purification of products.
Detailed Description
The invention provides a preparation method of a saturated monoboron compound, which comprises the following steps:
mixing an olefin compound, an alkali compound, a boron halide compound and an organic solvent, carrying out a boronization reaction, adding triethylamine and pinacol or adding triethylamine and 1,8-diaminonaphthalene, and carrying out an esterification reaction to obtain the saturated monoboron compound.
In the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.
In the invention, the reaction equation of the preparation method of the saturated monoboron compound is as follows:
Figure BDA0002728382220000021
note: the "base" in the reaction equation refers to the base compound.
In the present invention, the olefinic compound preferably has a structure represented by formula 1 or formula 2:
Figure BDA0002728382220000022
wherein R is 1 Is aryl, aromatic heterocycle or alkyl, R 2 、R 3 And R 4 Independently aryl, alkyl or hydrogen.
In the present invention, said R 1 Preferably beta-naphthalene, ferrocene, N-methylindole, phenyl, substituted phenyl or alkyl; the substituent in the substituted phenyl group is preferably methyl, fluorine, chlorine, bromine, tert-butyl, phenyl, trifluoromethyl, pentafluorophenyl or methylthio. The present invention is not limited to any particular substitution site for the substituent.
In the present invention, said R 2 、R 3 And R 4 Independently preferably hydrogen or a straight chain alkyl group.
In a specific embodiment of the present invention, the olefinic compound is styrene, 4-methylstyrene, 4-tert-butylstyrene, 4-trifluoromethylstyrene, 4-fluorostyrene, 4-chlorostyrene, 4-bromostyrene, 4-phenylstyrene, 2-methylstyrene, 2-chlorostyrene, 3-methylstyrene, 3-chlorostyrene, β -naphthylethylene, 2,3,4,5, 6-pentafluorostyrene, vinylferrocene, 4-methylthiostyrene, α -methylstyrene, α -n-butylstyrene, α -methyl-2 '-naphthylethylene, α -methyl-4' -methylthiostyrene, α -ethyl-4 '-methylstyrene, α -ethylmethylstyrene, 4' -methylstyrene, 4-bromostyrene, 2-chlorostyrene, 3-methylstyrene, 3-chlorostyrene, β -naphthylethylene, 2,3,4,5, 6-pentafluorostyrene, vinylferrocene, 4-methylthiostyrene, α -methylstyrene, α -n-butylstyrene, α -methyl-2 '-methylthiostyrene, α -methyl-ethyl-4' -methylstyrene, or α -ethylstyrene, Alpha-cyclopentyl-styrene, alpha-cyclohexyl-styrene, 1-methylene-1, 2,3, 4-tetrahydronaphthalene, 1-heptene, 1-octene, 2-methyl-1-heptene, methylcyclohexane, vinylcyclohexane, 3-cyclohexyl-1-propene, allylbenzene, 4-phenyl-1-butene, 4-phenyl-2-methyl-1-butene, 5-bromo-1-pentene, 6-bromo-1-hexene, 3-pinacol borate-1-propene, 3-phenylsulfide-1-propene, camphene, longifolene, (1' r, 4' r) -4-methylene-4 ' - (p-tolyl) -1,1' -bis (cyclohexane), 1-methyl-3- (prop-1-en-1-yl) -1H-indole, 3- (but-1-en-1-yl) -1-methyl-1H-indole, 1-methyl-3- (pent-1-en-1-yl) -1H-indole, 1-methyl-3- (4-phenylbut-1-en-1-yl) -1H-indole, 1-methyl-3- (pent-2-en-1-yl) -1H-indole, 1-methyl-3- (pent-3-en-1-yl) -1H-indole, 1-methyl-3- (pent-4-en-1-yl) -1H-indole, 2-octene, 6-chloro-2-hexene, cyclohexene, cycloheptene, 1-2, 2-tetramethylethylene, 4-octene, 1, 6-diphenyl-3-hexene or α -myrcene.
In the present invention, the basic compound is preferably diisopropylethylamine or isopropylamine, more preferably diisopropylethylamine; the boron halide is preferably boron tribromide, boron trichloride, or boron tribromide dimethylsulfide complex, more preferably boron tribromide; the organic solvent is preferably toluene, dichloromethane, 1, 2-dichloroethane or n-hexane.
In the present invention, the molar ratio of the olefin compound, the base compound and the boron halide compound is preferably 1: (1-6): (1 to 6), more preferably 1: (2-5): (2-5), most preferably 1: (3-4): (3-4). In the present invention, the ratio of the molar amount of the olefin compound to the volume of the organic solvent is preferably (0.2 to 0.3) mmol (1 to 3) mL.
In the present invention, the mixing is preferably performed by mixing the olefin compound, the alkali compound and the organic solvent and then adding the boron halide at a temperature of 0 ℃. In the present invention, the boron halide is preferably added in the form of a solution or as a pure substance; the method of adding the boron halide in the present invention is not particularly limited, and may be a method known to those skilled in the art.
In the present invention, the boronation reaction is preferably carried out in a protective atmosphere, preferably a nitrogen atmosphere or an argon atmosphere; the pressure of the protective atmosphere is preferably 1 atm; the temperature of the boronizing reaction is preferably 20-80 ℃, and the time of the boronizing reaction is preferably 1-24 h, more preferably 5-20 h, and most preferably 10-15 h. In the present invention, the boronation reaction is preferably carried out under stirring, and the stirring conditions are not particularly limited, and may be carried out by a method known to those skilled in the art.
In the present invention, the addition of the triethylamine and pinacol or the addition of the triethylamine and 1,8-diaminonaphthalene is preferably carried out under stirring conditions, and the stirring in the present invention is not particularly limited, and stirring conditions well known to those skilled in the art may be employed.
In the present invention, the molar ratio of the olefin compound to triethylamine is preferably 1: 3; the molar ratio of the olefinic compound to pinacol is preferably 1: 1.5; the molar ratio of the olefinic compound to 1,8-diaminonaphthalene is preferably 1: 1.5.
In the present invention, the esterification reaction is preferably carried out under stirring conditions, and the stirring conditions are not particularly limited in the present invention and are carried out by a process well known to those skilled in the art. In the present invention, the temperature of the esterification reaction is preferably room temperature, and the time of the esterification reaction is preferably 1 hour.
In the invention, the esterification reaction is to generate a more stable saturated monoboron compound, and is convenient to separate.
After the esterification reaction is completed, the invention also preferably comprises separation, and the invention does not limit the separation in any way and can carry out column chromatography and reduced pressure spin drying by adopting the process well known to the technical personnel in the field. In the embodiment of the present invention, in embodiments 1 to 15, a product system containing a saturated monoboron compound is directly obtained without separation, and a yield of the saturated monoboron compound in the product system is detected through a gas phase. If the product system needs to be separated and purified, the separation method is referred to.
The following examples are provided to illustrate the preparation of the saturated monoboron compounds of the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Diisopropylethylamine (as i Pr 2 NEt, 0.2mmol, 33. mu.L), dichloromethane (1mL) and styrene (1a, 0.2mmol, 23. mu.L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.2mmol, 0.2mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (NEt) 3 0.6mmol, 84. mu.L) and pinacol (pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h to give a product system containing the compound of formula 2 a. The GC-MS detection yield is 23 percent;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000041
example 2
Diisopropylethylamine (note as i Pr 2 NEt, 0.4mmol, 66. mu.L), dichloromethane (1mL) and styrene (1a, 0.2mmol, 23. mu.L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.2mmol, 0.2mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (NEt) 3 0.6mmol, 84. mu.L) and pinacol (pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h to give a product system containing the compound of formula 2 a. The GC-MS detection yield is 54 percent;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000042
example 3
Diisopropylethylamine (as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (1mL) and styrene (1a, 0.2mmol, 23. mu.L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.2mmol, 0.2mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (NEt) 3 0.6mmol, 84. mu.L) and pinacol (described aspinacol, 0.3mmol, 35.4mg) was stirred at room temperature for 1h to obtain a product system containing the compound of formula 2 a. The GC-MS detection yield is 32%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000051
example 4
Diisopropylethylamine (note as i Pr 2 NEt, 1.2mmol, 198. mu.L), dichloromethane (1mL) and styrene (1a, 0.2mmol, 23. mu.L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.2mmol, 0.2mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (NEt) 3 0.6mmol, 84. mu.L) and pinacol (pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h to give a product system containing the compound of formula 2 a. The GC-MS detection yield is 17 percent;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000052
example 5
Diisopropylethylamine (denoted as iPr) 2 NEt, 0.6mmol, 99. mu.L, methylene chloride (1mL) and styrene (1a, 0.2mmol, 23. mu.L) were mixed, a solution of boron tribromide in methylene chloride (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under a nitrogen (1atm) atmosphere for 12h, and triethylamine (NEt) 3 0.6mmol, 84. mu.L) and pinacol (pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h to give a product system containing the compound of formula 2 a. The GC-MS detection yield is 85%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000053
example 6
Diisopropylethylamine (denoted as iPr) 2 NEt, 0.6mmol, 99. mu.L, methylene chloride (1mL) and styrene (1a, 0.2mmol, 23. mu.L) were mixed, a solution of boron tribromide in methylene chloride (17% by mass, 0.6mmol, 0.6mL) was added at 0 ℃, stirred at room temperature under a nitrogen (1atm) atmosphere for 12 hours, and triethylamine (NEt) 3 0.6mmol, 84. mu.L) and pinacol (pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h to give a product system containing the compound of formula 2 a. The GC-MS detection yield is 70 percent;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000054
example 7
Diisopropylethylamine (designated as iPr) 2 NEt, 1.2mmol, 198. mu.L, methylene chloride (1mL) and styrene (1a, 0.2mmol, 23. mu.L) were mixed, a solution of boron tribromide in methylene chloride (17% by mass, 1.2mmol, 1.2mL) was added at 0 ℃, stirred at room temperature under a nitrogen (1atm) atmosphere for 12h, and triethylamine (NEt) 3 0.6mmol, 84. mu.L) and pinacol (pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h to give a product system containing the compound of formula 2 a. The GC-MS detection yield is 46 percent;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000061
example 8
Diisopropylethylamine (designated as iPr) 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (1mL) and styrene (1a, 0.2mmol, 23. mu.L) were mixed, boron tribromide (0.3mmol, 57. mu.L) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, triethylamine (NEt) 3 ，0.6mmol84 mu.L) and pinacol (pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h to obtain a product system containing the compound of formula 2 a. The GC-MS detection yield is 70 percent;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000062
example 9
Diisopropylethylamine (designated as iPr) 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (1mL) and styrene (1a, 0.2mmol, 23. mu.L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (NEt) 3 0.6mmol, 84. mu.L) and pinacol (pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h to give a product system containing the compound of formula 2 a. The GC-MS detection yield is 75 percent;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000063
example 10
Diisopropylamine (as i Pr 2 NH, 0.6mmol, 85. mu.L), dichloromethane (1mL) and styrene (1a, 0.2mmol, 23. mu.L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h to give a product system containing the compound of formula 2 a. The GC-MS detection yield is 24 percent;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000064
example 11
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), toluene (as Tol., 1mL) and styrene (as 1a, 0.2mmol, 23. mu.L) were mixed, boron tribromide (0.3mmol, 57. mu.L) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) atmosphere for 12h, and triethylamine (as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h to give a product system containing the compound of formula 2 a. The GC-MS detection yield is 31 percent;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000071
example 12
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), 1, 2-dichloroethane (1mL DCE) and styrene (1a, 0.2mmol, 23. mu.L) were mixed, boron tribromide (0.3mmol, 57. mu.L) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) atmosphere for 12h, and triethylamine (NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h to give a product system containing the compound of formula 2 a. The GC-MS detection yield is 12 percent;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000072
example 13
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L, n-hexane (1mL, n-Hex) and styrene (1a, 0.2mmol, 23. mu.L) were mixed, boron tribromide (0.3mmol, 57. mu.L) was added at 0 ℃, stirring was carried out at room temperature under a nitrogen (1atm) atmosphere for 12h, and triethylamine (NEt, n-hexane) was added 3 ，0.6mmol, 84. mu.L) and pinacol (pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h to obtain a product system containing the compound of formula 2 a. The GC-MS detection yield is 26 percent;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000073
example 14
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and styrene (denoted as 1a, 0.2mmol, 23. mu.L) were mixed, a solution of boron tribromide dimethylsulfide complex in dichloromethane (concentration 1M, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) atmosphere for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h to give a product system containing the compound of formula 2 a. The GC-MS detection yield is 23 percent;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000074
example 15
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and styrene (denoted as 1a, 0.2mmol, 23. mu.L) were mixed, a solution of boron tribromide dimethylsulfide complex in dichloromethane (concentration 1M, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at 40 ℃ under nitrogen (1atm) atmosphere for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h to give a product system containing the compound of formula 2 a. The GC-MS detection yield is 41 percent;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000081
the compounds with the structure shown in the formula 2a prepared in the embodiments 1-15 are colorless oily 1- (pinacolborate) phenylethane, and the characterization data are as follows: 1 H NMR(400MHz,Chloroform-d)δ7.30–7.21(m,4H),7.19–7.11(m,1H),2.76(t,J＝8.0Hz,2H),1.23(s,12H),1.15(t,J＝8.0Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ143.4,127.2,127.0,82.1,28.9,23.8. 11 B NMR(128MHz,Chloroform-d)δ33.69。
example 16
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 4-methylstyrene (denoted as 1b, 0.2mmol, 26.3. mu.L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of the structure shown in formula 2b (colorless oil, 1- (pinacolboronic acid ester) -4' -methyl-phenylethane). The isolated yield was 61%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000082
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.09(q,J＝8.0Hz,4H),2.71(t,J＝8.0Hz,2H),2.31(s,3H),1.24(s,12H),1.16–1.09(m,2H). 13 C NMR(101MHz,Chloroform-d)δ141.5,134.9,129.0,127.9,83.2,29.6,24.9,21.1. 11 B NMR(128MHz,Chloroform-d)δ33.64。
example 17
Diisopropylethylamine (note as i Pr 2 NEt，06mmol, 99. mu.L), dichloromethane (denoted DCM, 1mL) and 4-tert-butylstyrene (denoted 1c, 0.2mmol, 36.4. mu.L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under a nitrogen (1atm) atmosphere for 12h, triethylamine (denoted NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of formula 2c (colorless oil, 1- (pinacolboronic acid ester) -4' -tert-butyl-phenylethane). The isolated yield was 59%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000083
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.32–7.27(m,2H),7.19–7.14(m,2H),2.72(t,J＝8.0Hz,2H),1.31(s,9H),1.23(s,12H),1.18–1.12(t,J＝8.0Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ148.3,141.4,127.7,125.1,83.1,34.3,31.4,29.4,24.8. 11 B NMR(128MHz,Chloroform-d)δ33.59。
example 18
Diisopropylethylamine (as i Pr 2 NEt, 0.6mmol, 99. mu.L, dichloromethane (as DCM, 1mL) and 4-trifluoromethylstyrene (as 1d, 0.2mmol, 29.6. mu.L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under a nitrogen (1atm) atmosphere for 12h, and triethylamine (as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give the compound of formula 2d (colorless oil, 1- (pinacolboronic acid ester) -4' -trifluoromethyl-phenylethane). The isolated yield was 72%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000091
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.56–7.48(m,2H),7.37–7.29(m,2H),2.80(t,J＝8.1Hz,2H),1.22(s,12H),1.15(t,J＝8.0Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ148.5,128.3,125.0(q,J＝3.8Hz),83.2,29.8,24.7. 11 B NMR(128MHz,Chloroform-d)δ34.07. 19 F NMR(376MHz,Chloroform-d)δ-62.28。
example 19
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 4-fluorostyrene (denoted as 1e, 0.2mmol, 23.7. mu.L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give the compound of formula 2e (colorless oil, 1- (pinacolboronic acid ester) -4' -fluoro-phenylethane). The isolated yield was 72%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000092
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.19–7.13(m,2H),6.99–6.90(m,2H),2.72(t,J＝8.0Hz,2H),1.21(s,12H),1.12(t,J＝8.0Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ161.2(d,J＝242.6Hz),140.0(d,J＝3.2Hz),129.4(d,J＝7.7Hz),114.9(d,J＝21.0Hz),83.2,29.2,24.9. 11 B NMR(128MHz,Chloroform-d)δ33.97. 19 F NMR(376MHz,Chloroform-d)δ-118.41(tt,J＝9.5,5.5Hz)。
example 20
Diisopropylethylamine (as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 4-chlorostyrene (denoted as 1f, 0.2mmol, 25.5. mu.L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give the compound represented by the formula 2f (colorless oil, 1- (pinacolboronic acid ester) -4' -chloro-phenylethane). The isolated yield was 56%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000101
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.24–7.19(m,2H),7.16–7.11(m,2H),2.71(t,J＝8.1Hz,2H),1.21(s,12H),1.11(t,J＝8.1Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ142.8,131.2,129.4,128.2,83.2,29.3,24.8. 11 B NMR(128MHz,Chloroform-d)δ33.42。
example 21
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 4-bromostyrene (denoted as 1g, 0.2mmol, 26.3. mu.L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and the product was purified by silica gel column chromatography using petroleum ether: after ethyl acetate (volume ratio of 30:1) is used as eluent for elution,the solvent was spin-dried under reduced pressure to give the compound of formula 2g (colorless oil, 1- (pinacolboronic acid ester) -4' -bromo-phenylethane). The isolated yield was 63%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000102
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.41–7.33(m,2H),7.14–7.05(m,2H),2.69(t,J＝8.1Hz,2H),1.21(s,12H),1.11(t,J＝8.0Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ143.4,131.2,129.8,119.2,83.2,29.4,24.8. 11 B NMR(128MHz,Chloroform-d)δ33.75。
example 22
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L, dichloromethane (shown as DCM, 1mL) and 4-phenylstyrene (shown as 1h, 0.2mmol, 26.3. mu.L) are mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) is added at 0 ℃, stirring is carried out under nitrogen (1atm) at room temperature for 12h, and triethylamine (shown as NEt) is added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give the compound of formula 2h (colorless oil, 1- (pinacolboronic acid ester) -4' -phenyl-phenylethane). The isolated yield was 67%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000103
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.65–7.56(m,2H),7.54–7.50(m,2H),7.43(dd,J＝8.4,6.9Hz,2H),7.40–7.28(m,3H),2.85–2.78(m,2H),1.25(s,12H),1.23–1.18(m,2H). 13 C NMR(101MHz,Chloroform-d)δ143.6,141.3,138.5,128.7,128.5,127.0,127.0,126.9,83.2,29.6,24.9. 11 B NMR(128MHz,Chloroform-d)δ34.49。
example 23
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 2-methylstyrene (denoted as 1i, 0.2mmol, 26.4. mu.L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give the compound represented by formula 2i (colorless oil, 1- (pinacolboronic acid ester) -2' -methyl-phenylethane). The isolated yield was 50%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000111
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.19(dd,J＝6.1,3.0Hz,1H),7.10(pd,J＝6.5,1.9Hz,3H),2.72(t,J＝8.0Hz,2H),2.32(s,1H),1.24(s,12H),1.11(t,J＝8.0Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ142.6,135.9,130.1,128.2,125.9,125.7,83.2,27.3,24.9,19.3. 11 B NMR(128MHz,Chloroform-d)δ33.92。
example 24
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 2-chlorostyrene (denoted as 1j, 0.2mmol, 25.5. mu.L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (designated as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1 hour, and then purified by silica gel column chromatographyThe material adopts petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of formula 2j (colorless oil, 1- (pinacolboronic acid ester) -2' -methyl-phenylethane). The isolated yield was 75%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000112
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.38–7.25(m,2H),7.13(dtd,J＝25.3,7.5,1.7Hz,2H),2.84(t,J＝8.0Hz,2H),1.24(s,12H),1.15(t,J＝8.0Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ141.8,133.8,129.7,129.3,126.9,126.6,83.1,27.7,24.8. 11 B NMR(128MHz,Chloroform-d)δ33.80。
example 25
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 3-methylstyrene (denoted as 1k, 0.2mmol, 26.4. mu.L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give the compound of formula 2k (colorless oil, 1- (pinacolboronic acid ester) -3' -methyl-phenylethane). The isolated yield was 65%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000121
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.15(t,J＝7.5Hz,1H),7.07–6.94(m,3H),2.72(t,J＝8.0Hz,2H),2.32(s,3H),1.23(s,12H),1.16–1.12(m,2H). 13 C NMR(101MHz,Chloroform-d)δ144.5,137.8,129.0,128.2,126.4,125.2,83.2,30.0,25.0,21.5. 11 B NMR(128MHz,Chloroform-d)δ33.71。
example 26
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 3-chlorostyrene (denoted as 1L, 0.2mmol, 25.5. mu.L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give the compound of formula 2l (colorless oil, 1- (pinacolboronic acid ester) -3' -chloro-phenylethane). The isolated yield was 47%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000122
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.25–7.05(m,4H),2.72(t,J＝8.0Hz,2H),1.22(s,12H),1.12(t,J＝8.0Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ146.5,133.9,129.4,128.3,126.3,125.7,83.2,29.7,24.8. 11 B NMR(128MHz,Chloroform-d)δ33.95。
example 27
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and beta-naphthylethylene (denoted as 1m, 0.2mmol, 30.8mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, then silica gel was addedPurifying the product by column chromatography, wherein petroleum ether: after ethyl acetate (volume ratio 30:1) was used as an eluent for elution, the solvent was spin-dried under reduced pressure to obtain a compound having a structure represented by formula 2m (white solid, 1- (pinacolboronic acid ester) - β -phenylethane). The isolated yield was 82%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000123
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.85–7.76(m,3H),7.71–7.66(m,1H),7.49–7.38(m,3H),2.96(t,J＝8.1Hz,2H),1.30–1.24(m,2H),1.25(s,12H). 13 C NMR(101MHz,Chloroform-d)δ142.1,133.8,132.0,127.8,127.7,127.5,127.4,125.8,125.8,125.0,83.2,30.2,24.9. 11 B NMR(128MHz,Chloroform-d)δ33.73。
example 28
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 2,3,4,5, 6-pentafluorostyrene (denoted as 1n, 0.2mmol, 24.8. mu.L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) atmosphere for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after ethyl acetate (volume ratio of 30:1) was used as an eluent for elution, the solvent was spin-dried under reduced pressure to obtain a compound having a structure represented by formula 2n (colorless oil, 1- (pinacolboronic acid ester) -2',3',4',5',6' -pentafluorophenylethane). The isolated yield was 70%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000131
the characterization data are: 1H NMR (400MHz, Chloroform-d) δ 2.89-2.63 (m,1H), 1.30-1.28 (m,2H), 1.27-1.22 (m,12H), 1.14-1.06 (m,1H), 13C NMR (101MHz, Chloroform-d) δ 84.1,83.4,24.7,24.7,24.5,16.9,15.4.11B NMR (128MHz, Chloroform-d) δ 33.43.19F NMR (376MHz, Chloroform-d) δ -143.43-143.56 (m), -144.38(dd, J ═ 22.3,8.3Hz), -158.88(t, J ═ 20.8Hz), -159.38(t, J ═ 20.8Hz), -163.06 (163.78 (m).
Example 29
Diisopropylethylamine (designated as iPr2NEt, 0.6mmol, 99 μ L), dichloromethane (designated as DCM, 1mL) and vinylferrocene (designated as 1o, 0.2mmol, 44.4 μ L) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under a nitrogen (1atm) atmosphere for 12h, triethylamine (designated as NEt3, 0.6mmol, 84 μ L) and 1,8-Diaminonaphthalene (designated as 1,8-Diaminonaphthalene, 0.3mmol, 35.4mg) were added and stirred at room temperature for 1h, and the product was purified by silica gel column chromatography using petroleum ether: after ethyl acetate (volume ratio of 30:1) is used as eluent for elution, the solvent is decompressed and dried in a spinning mode to obtain a compound with a structure shown in a formula 2o (red oily matter, 2- [ 2-ethyl ferrocene ] -2, 3-dihydro-1H-naphtho [1,8-DE ] -1,3, 2-diazole boron). The isolated yield was 34%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000132
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.10(dd,J＝8.3,7.3Hz,2H),7.01(dd,J＝8.3,1.1Hz,2H),6.29(dd,J＝7.3,1.1Hz,2H),5.60(s,2H),4.12(s,6H),4.07(t,J＝1.8Hz,2H),2.51(t,J＝8.0Hz,2H),1.18–1.12(m,2H). 13 C NMR(101MHz,Chloroform-d)δ141.2,136.4,127.7,117.5,105.6,91.1,68.6,67.9,67.3,24.7. 11 B NMR(128MHz,Chloroform-d)δ32.37.HRMS(ESI)m/z:[M] + calcdforC 22 H 21 BFeN 2 + :380.1147；found:380.1159。
example 30
Diisopropylethylamine (as i Pr 2 NEt, 0.6mmol, 99. mu.L), methylene chloride(shown as DCM, 1mL) and 4-methylthiostyrene (shown as 1p, 0.2mmol, 30mg) were mixed, a solution of boron tribromide in dichloromethane (mass concentration 17%, 0.3mmol, 0.3mL) was added at 0 deg.C, stirring was carried out at 60 deg.C for 24h under a nitrogen (1atm) atmosphere, and triethylamine (shown as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of the formula 2p (colorless oil, 1- (pinacolboronic acid ester) -4' methylthiophenylethane). The isolated yield was 36%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000141
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.21–7.11(m,4H),2.71(t,J＝8.0Hz,2H),2.45(s,3H),1.22(s,12H),1.11(t,J＝8.0Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ141.7,134.8,128.6,127.3,83.1,29.4,24.8,16.5. 11 B NMR(128MHz,Chloroform-d)δ33.52。
example 31
Diisopropylethylamine (as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and alpha-methylstyrene (denoted as 1aa, 0.2mmol, 23.6mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 in terms of volume ratio) as an eluent, the solvent was spin-dried under reduced pressure to give the compound represented by the formula 2aa (colorless oil, 1- (pinacolboronic acid ester) -2-methyl-2-phenylethane). The isolated yield was 47%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000142
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.28–7.26(m,1H),7.25–7.21(m,3H),7.17–7.12(m,1H),3.03(dt,J＝8.2,6.9Hz,1H),1.30–1.25(m,4H),1.16(s,12H),1.14(s,1H). 13 C NMR(101MHz,Chloroform-d)δ149.4,128.3,126.8,125.8,83.1,35.9,25.0,24.9,24.8. 11 B NMR(128MHz,Chloroform-d)δ33.70。
example 32
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and alpha-n-butylstyrene (denoted as 1ab, 0.2mmol, 32mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 deg.C, stirring was carried out at 60 deg.C under a nitrogen (1atm) atmosphere for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of the formula 2ab (colorless oil, 1- (pinacolboronic acid ester) -2-n-butyl-2-phenylethane). The isolated yield was 59%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000143
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.27–7.21(m,2H),7.20–7.17(m,2H),7.15–7.10(m,1H),2.81(tt,J＝8.6,6.8Hz,1H),1.57(ddd,J＝10.4,5.6,3.5Hz,1H),1.36–1.12(m,6H),1.09(s,12H),0.82(t,J＝7.2Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ147.8,128.2,127.6,125.8,83.0,41.6,39.3,30.0,24.8,22.8,14.1. 11 B NMR(128MHz,Chloroform-d)δ33.20.HRMS(ESI)m/z:[M+Na] + calcdforC 18 H 29 BO 2 Na + :311.2158；found:311.2158。
example 33
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and alpha-n-butylstyrene (denoted as 1ac, 0.2mmol, 36mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 deg.C, stirring was carried out at 60 deg.C under a nitrogen (1atm) atmosphere for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and the product was purified by silica gel column chromatography using petroleum ether: after ethyl acetate (volume ratio 30:1) was used as an eluent for elution, the solvent was spin-dried under reduced pressure to obtain a compound having a structure represented by formula 2ac (colorless oil, 1- (pinacolboronic acid ester) -2, 2-diphenylethane). The isolated yield was 57%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000151
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.32–7.19(m,8H),7.16–7.09(m,2H),4.28(t,J＝8.5Hz,1H),1.60(d,J＝8.5Hz,2H),1.05(s,12H). 13 C NMR(101MHz,Chloroform-d)δ146.7,128.4,127.8,126.0,83.3,46.7,24.7. 11 B NMR(128MHz,Chloroform-d)δ32.83。
example 34
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and alpha-methyl-2' -naphthylethylene (denoted as 1ad, 0.2mmol, 33.6mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 deg.C, stirred at 60 deg.C under nitrogen (1atm) for 12h, triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: ethyl acetate (volume ratio of30:1) as an eluent, and then spin-drying the solvent under reduced pressure to obtain the compound with the structure shown in the formula 2ad (colorless oily substance, 1- (pinacolborate) -2-methyl-2-beta' -naphthyl ethane). The isolated yield was 76%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000152
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.83–7.75(m,3H),7.68(s,1H),7.48–7.38(m,3H),3.24(h,J＝7.2Hz,1H),1.39(dd,J＝6.9,1.0Hz,3H),1.30–1.26(m,2H),1.16(s,12H). 13 C NMR(101MHz,Chloroform-d)δ146.7,133.6,132.1,127.7,127.6,127.5,125.8,125.6,124.9,124.4,83.0,35.9,24.7,24.7,24.7. 11 B NMR(128MHz,Chloroform-d)δ32.69。
example 35
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and alpha-methyl-4' -methylthiostyrene (denoted as 1ac, 0.2mmol, 32.8mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 deg.C, stirring was carried out at 60 deg.C under a nitrogen (1atm) atmosphere for 24h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of the formula 2ae (colorless oil, 1- (pinacolboronic acid ester) -2-methyl-2-4' -methylthiophenyl ethane). The isolated yield was 60%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000161
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.21–7.14(m,4H),3.00(h,J＝7.2Hz,1H),2.45(s,3H),1.25(d,J＝6.9Hz,3H),1.16(s,11H),1.12(dd,J＝7.8,2.3Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ146.7,135.0,127.4,127.3,83.1,35.4,24.9,24.9,24.8,16.6. 11 B NMR(128MHz,Chloroform-d)δ34.08。
example 36
Diisopropylethylamine (as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted DCM, 1mL) and alpha-ethyl-4' -methylstyrene (denoted 1af, 0.2mmol, 29.2mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, triethylamine (denoted NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 in terms of volume ratio) as an eluent, the solvent was spin-dried under reduced pressure to give the compound represented by the formula 2af (colorless oil, 1- (pinacolboronic acid ester) -2-ethyl-2-4' -methylphenylethane). The isolated yield was 60%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000162
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.11–7.02(m,4H),2.70(tdd,J＝8.5,7.2,5.8Hz,1H),2.30(s,3H),1.65–1.56(m,2H),1.11(s,14H),0.77(t,J＝7.4Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ144.4,135.1,128.8,127.4,83.0,42.9,32.3,24.82,24.80,21.1,12.4. 11 B NMR(128MHz,Chloroform-d)δ34.12。
example 37
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted DCM, 1mL) and alpha-cyclopentyl-styrene (denoted 1ag, 0.2mmol, 34.4mg) were combined, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 deg.C, and the mixture was stirred at room temperature under a nitrogen (1atm) atmosphere for 12hAdding triethylamine (as NEt) 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of the structure represented by formula 2ag (colorless oil, 1- (pinacolboronic acid ester) -2-cyclopentyl-2-phenylethane). The isolated yield was 63%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000171
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.25–7.16(m,4H),7.14–7.09(m,1H),2.58(ddd,J＝10.9,9.4,5.2Hz,1H),2.01–1.81(m,2H),1.56–1.46(m,2H),1.42(dp,J＝8.3,2.8Hz,1H),1.34–1.23(m,4H),1.16–1.08(m,2H),1.01(s,12H). 13 C NMR(101MHz,Chloroform-d)δ147.4,128.0,127.9,125.7,82.9,49.2,47.4,31.6,31.5,25.4,25.3,24.8,24.6. 11 B NMR(128MHz,Chloroform-d)δ33.47.HRMS(ESI)m/z:[M+Na] + calcdfor C 19 H 29 BO 2 Na + :323.2158；found:323.2159。
example 38
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted DCM, 1mL) and alpha-cyclohexyl-styrene (denoted 1ah, 0.2mmol, 37.2mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 deg.C, stirred at room temperature under nitrogen (1atm) for 12h, triethylamine (denoted NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of the structure shown by formula 2ah (colorless oil, 1- (pinacolboronic acid ester) -2-cyclohexyl-2-phenylethane). The isolated yield was 63%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000172
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.24–7.20(m,2H),7.17–7.09(m,3H),2.60(ddd,J＝10.7,7.7,5.8Hz,1H),1.89–1.84(m,1H),1.73(ddt,J＝12.8,5.5,2.4Hz,1H),1.49–1.17(m,8H),1.01(d,J＝5.4Hz,12H),0.97–0.72(m,1H). 13 C NMR(101MHz,Chloroform-d)δ1146.4,128.5,127.8,125.7,82.9,47.6,45.2,31.2,31.0,26.6,24.7,24.6. 11 B NMR(128MHz,Chloroform-d)δ33.50.HRMS(ESI)m/z:[M+H] + calcdforC 20 H 32 BO 2 + :315.2495；found:315.2510。
example 39
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted DCM, 1mL) and 1-methylene-1, 2,3, 4-tetrahydronaphthalene (denoted 1ai, 0.2mmol, 28.8mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under a nitrogen (1atm) atmosphere for 12h, and triethylamine (denoted NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after ethyl acetate (volume ratio of 30:1) was used as an eluent for elution, the solvent was spin-dried under reduced pressure to give a compound of the structure represented by formula 2ai (colorless oil, 4,4,5, 5-tetramethyl-2- (((1,2,3, 4-tetrahydronaphthalen-1-yl) methyl) -1,3, 2-dioxaborane, isolated in 37% yield;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000181
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.26–7.20(m,1H),7.15–7.00(m,3H),3.08(dq,J＝11.1,5.7Hz,1H),2.84–2.67(m,2H),2.01–1.81(m,2H),1.78–1.68(m,1H),1.67–1.57(m,3H),1.34–1.28(m,1H),1.25(d,J＝8.9Hz,12H),1.13(dd,J＝15.6,9.6Hz,1H). 13 C NMR(101MHz,Chloroform-d)δ142.9,136.9,128.9,128.2,125.5,125.3,83.1,33.8,31.1,29.8,25.0,24.7,20.4. 11 B NMR(128MHz,Chloroform-d)δ34.17。
example 40
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 1-heptene (denoted as 1ba, 0.2mmol, 19.6mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give the compound of formula 2ba (colorless oil, 1- (pinacolboronic acid ester) heptane). The isolated yield was 53%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000182
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ1.48–1.36(m,2H),1.30–1.25(m,8H),1.24(s,12H),0.90–0.84(m,3H),0.76(t,J＝7.8Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ83.0,32.5,32.0,29.2,25.0,24.2,22.8,14.2. 11 B NMR(128MHz,Chloroform-d)δ34.05。
example 41
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 1-octene (denoted as 1bb, 0.2mmol, 22.4mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted as NEt) was added 3 ，0.6mmol84 μ L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of the structure represented by formula 2bb (colorless oil, 1- (pinacolboronic acid ester) octane). The isolated yield was 52%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000183
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ1.42–1.34(m,3H),1.29–1.24(m,9H),1.23(s,12H),0.86(t,J＝6.8Hz,3H),0.75(t,J＝7.7Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ82.9,32.5,32.0,29.5,29.3,24.9,24.1,22.8,14.2. 11 B NMR(128MHz,Chloroform-d)δ33.64。
example 42
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L, dichloromethane (as DCM, 1mL) and 2-methyl-1-heptene (as 1bc, 0.2mmol, 22.4mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature for 12h under a nitrogen (1atm) atmosphere, triethylamine (as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (volume ratio 30:1) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of the structure represented by formula 2bc (colorless oil, 1- (pinacolboronic acid ester) -2-methylheptane). The isolated yield was 51%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000191
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ1.72–1.60(m,1H),1.34–1.25(m,5H),1.24(s,12H),1.20–1.10(m,2H),0.94–0.78(m,7H),0.63(dd,J＝15.3,8.3Hz,1H). 13 C NMR(101MHz,Chloroform-d)δ82.9,39.7,32.2,29.6,27.1,25.0,24.9,22.8,22.5,14.2. 11 B NMR(128MHz,Chloroform-d)δ33.84。
example 43
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and methylenecyclohexane (denoted as 1bd, 0.2mmol, 19.2mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 in terms of volume ratio) as an eluent, the solvent was spin-dried under reduced pressure to give a compound represented by the formula 2bd (colorless oil, 1- (pinacolboronic acid ester) -1-cyclohexylmethane). The isolated yield was 45%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000192
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ1.73–1.62(m,6H),1.48(m,1H),1.24(s,12H),1.15–1.07(m,1H),0.91(m,3H),0.70(d,J＝7.2Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ83.0,36.1,34.4,31.7,26.7,26.5,25.0,22.8,14.3. 11 B NMR(128MHz,Chloroform-d)δ34.17。
example 44
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted DCM, 1mL) and vinylcyclohexane (denoted 1be, 0.2mmol, 22mg) were combined, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 deg.C, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of the formula 2be (colorless oil, 1- (pinacolboronic acid ester) -1-cyclohexylethane). The isolated yield was 63%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000201
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ1.76–1.57(m,6H),1.31–1.27(m,2H),1.24(d,J＝1.5Hz,12H),1.19–1.05(m,3H),0.84(dd,J＝12.9,9.6Hz,2H),0.78–0.70(m,2H). 13 C NMR(101MHz,Chloroform-d)δ83.0,40.1,33.1,31.5,26.9,26.6,24.9. 11 BN MR(128MHz,Chloroform-d)δ34.37。
example 45
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 3-cyclohexyl-1-propene (denoted as 1bf, 0.2mmol, 24.8mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 in terms of volume ratio) as an eluent, the solvent was spin-dried under reduced pressure to give the compound represented by the formula 2bf (colorless oil, 1- (pinacolboronic acid ester) -3-cyclohexylpropane). The isolated yield was 63%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000202
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ1.72–1.60(m,5H),1.47–1.36(m,2H),1.24(s,12H),1.22–1.07(m,6H),0.92–0.80(m,2H),0.73(t,J＝7.8Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ82.9,40.5,37.6,33.5,26.9,26.5,24.9,21.4. 11 B NMR(128MHz,Chloroform-d)δ34.43。
example 46
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and allylbenzene (denoted as 1bg, 0.2mmol, 23.6mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give the compound of formula 2bg (colorless oil, 1- (pinacolboronic acid ester) -3-phenylpropane). The isolated yield was 66%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000203
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.22–7.15(m,2H),7.13–7.05(m,2H),2.86–2.31(m,2H),1.66(pd,J＝7.8,1.5Hz,2H),1.16(d,J＝1.5Hz,12H),0.79–0.71(m,2H). 13 C NMR(101MHz,Chloroform-d)δ141.6,127.5,127.1,124.5,81.9,37.5,28.6,25.0,23.8. 11 B NMR(128MHz,Chloroform-d)δ34.19。
example 47
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted DCM, 1mL) and 4-phenyl-1-butene (denoted 1bh, 0.2mmol, 26.4mg) were combined and a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃ under nitrogen (1atm)Stirred at room temperature for 12h under an atmosphere, triethylamine (noted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of formula 2bh (colorless oil, 1- (pinacolboronic acid ester) -4-phenylbutane). The isolated yield was 48%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000211
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.31–7.23(m,2H),7.21–7.13(m,3H),2.61(t,J＝8.0Hz,2H),1.77–1.56(m,2H),1.55–1.42(m,2H),1.24(s,12H),0.82(t,J＝7.8Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ143.1,128.5,128.3,125.6,83.0,35.9,34.3,25.0,23.9. 11 B NMR(128MHz,Chloroform-d)δ34.10。
example 48
Diisopropylethylamine (as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 4-phenyl-2-methyl-1-butene (denoted as 1bi, 0.2mmol, 26.4mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under a nitrogen (1atm) atmosphere for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of the formula 2bi (colorless oil, 1- (pinacolboronic acid ester) -2-methyl-4-phenylbutane). The isolated yield was 48%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000212
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.31–7.23(m,2H),7.20–7.13(m,3H),2.62(dp,J＝10.1,7.4Hz,2H),1.87–1.73(m,1H),1.65–1.58(m,1H),1.51(dddd,J＝13.5,10.1,7.4,6.3Hz,1H),1.25(s,12H),0.99(d,J＝6.6Hz,3H),0.91(dd,J＝15.4,5.8Hz,1H),0.73(dd,J＝15.3,8.3Hz,1H). 13 C NMR(101MHz,Chloroform-d)δ143.3,128.4,128.3,125.6,83.0,41.6,33.9,29.5,25.0,24.9,22.4. 11 B NMR(128MHz,Chloroform-d)δ33.66。
example 49
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 5-bromo-1-pentene (denoted as 1bj, 0.2mmol, 29.8mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 deg.C, stirred at room temperature under nitrogen (1atm) for 12h, triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of formula 2bj (colorless oil, 1- (pinacolboronic acid ester) -5-bromo-n-pentane). The isolated yield was 43%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000221
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ3.39(t,J＝6.9Hz,2H),1.86(q,J＝6.8,6.4Hz,2H),1.43(p,J＝3.7Hz,4H),1.24(s,12H),0.82–0.74(m,2H). 13 C NMR(101MHz,Chloroform-d)δ83.1,34.1,32.8,31.6,30.9,30.3,25.0,23.3. 11 B NMR(128MHz,Chloroform-d)δ33.86。
example 50
Diisopropylethylamine (note as i Pr 2 NEt，0.6mmol，99 μ L), dichloromethane (noted DCM, 1mL) and 6-bromo-1-hexene (noted 1bk, 0.2mmol, 32.6mg) were combined, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (noted NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (volume ratio 30:1) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of formula 2bk (colorless oil, 1- (pinacolboronic acid ester) -6-bromo-n-hexane). The isolated yield was 43%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000222
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ3.39(t,J＝6.9Hz,2H),1.84(p,J＝7.0Hz,2H),1.46–1.37(m,4H),1.34–1.29(m,2H),1.24(s,12H),0.77(t,J＝7.7Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ83.0,34.1,32.9,31.5,28.1,25.0,23.9. 11 B NMR(128MHz,Chloroform-d)δ34.35。
example 51
Diisopropylethylamine (as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 3-pinacolborate-1-propene (denoted as 1bl, 0.2mmol, 33.6mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of formula 2bl (colorless oil, 1- (pinacolboronic acid ester) propane). The isolated yield was 44%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000223
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ1.53(tt,J＝8.1,7.2Hz,2H),1.23(s,24H),0.81(t,J＝7.9Hz,4H). 13 C NMR(101MHz,Chloroform-d)δ82.9,24.9,18.7. 11 B NMR(128MHz,Chloroform-d)δ34.26。
example 52
Diisopropylethylamine (as i Pr 2 NEt, 0.6mmol, 99. mu.L, dichloromethane (1mL, as DCM), and 3-phenylene sulfide-1-propene (1 bm, 0.2mmol, 32.6mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature for 12h under a nitrogen (1atm) atmosphere, triethylamine (1atm, as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of the structure represented by formula 2bm (colorless oil, 1- (pinacolboronic acid ester) -3-phenylthiolethylpropane). The isolated yield was 86%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000231
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.41–7.31(m,2H),7.28–7.22(m,2H),7.14(ddt,J＝7.9,6.7,1.3Hz,1H),2.96–2.90(m,2H),1.77(p,J＝7.6Hz,2H),1.24(s,12H),0.92(t,J＝7.7Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ137.3,128.9,128.8,125.6,83.2,35.7,25.0,24.1. 11 B NMR(128MHz,Chloroform-d)δ33.61。
example 53
Diisopropylethylamine (as i Pr 2 NEt，0.6mmol，99 μ L), dichloromethane (DCM, 1mL) and camphene (1 bn, 0.2mmol, 27.2mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred under nitrogen (1atm) at room temperature for 24h, triethylamine (NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: eluting with ethyl acetate (volume ratio of 30:1), and spin-drying the solvent under reduced pressure to obtain the compound of formula 2bn (colorless oil, 2- (((4R) -3,3- (dimethylbicyclo [2.2.1 ]))]Hept-2-yl) methyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane. The isolated yield was 57%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000232
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ2.04–1.99(m,1H),1.78–1.60(m,4H),1.56–1.48(m,1H),1.40–1.32(m,2H),1.22(s,12H),1.20–1.15(m,1H),1.08(dt,J＝9.5,1.7Hz,1H),0.93(s,3H),0.83–0.78(m,1H),0.75(s,3H),0.64(dd,J＝15.5,8.7Hz,1H). 13 C NMR(101MHz,Chloroform-d)δ82.7,49.7,49.3,49.0,46.4,45.9,44.0,40.5,37.0,36.9,35.4,31.9,29.7,27.6,25.5,24.8,24.7,24.6,24.1,21.8,19.9. 11 B NMR(128MHz,Chloroform-d)δ33.46。
example 54
Diisopropylethylamine (as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and longifolene (denoted as 1bo, 0.2mmol, 27.2mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 24h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and the product was purified by silica gel column chromatography using petroleum ether: eluting with ethyl acetate (volume ratio of 30:1), and collecting eluateThe solvent was spin-dried under reduced pressure to give a compound of the structure represented by formula 2bo (colorless oil, 4,4,5, 5-tetramethyl-2- ((((((1R, 4R, 8aS) -4,8, 8-trimethyldecahydro-1, 4-methylnaphthalen-9-yl) methyl) -1,3, 2-dioxaborane), isolated in 63% yield;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000241
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ2.21(tdd,J＝7.2,3.9,1.3Hz,1H),1.99–1.94(m,1H),1.88(d,J＝3.4Hz,1H),1.75–1.63(m,2H),1.54–1.44(m,3H),1.42–1.36(m,2H),1.35–1.28(m,4H),1.24(s,12H),0.98(s,3H),0.95(s,3H),0.92–0.84(m,1H),0.73(s,3H),0.66(dd,J＝15.1,9.2Hz,1H). 13 C NMR(101MHz,Chloroform-d)δ82.8,61.5,45.5,44.8,43.6,42.9,40.6,40.2,33.4,32.9,29.7,26.2,25.0,24.9,24.7,21.9,20.9. 11 B NMR(128MHz,Chloroform-d)δ33.93.HRMS(ESI)m/z:[M+H] + calcdforC 21 H 38 BO 2 + :323.2965；found:323.2976。
example 55
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (described as DCM, 1mL) and (1'r, 4' r) -4-methylene-4 '- (p-tolyl) -1,1' -bi (cyclohexane) (described as 1bp, 0.2mmol, 47.6mg) were combined, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 deg.C, stirring was carried out at room temperature under a nitrogen (1atm) atmosphere for 24h, and triethylamine (described as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (volume ratio: 30:1) as an eluent, the solvent was spin-dried under reduced pressure to give a compound having a structure represented by the formula 2bp (white solid, 4,4,5, 5-tetramethyl-2- ((((1'r, 4' r) -4'- (p-tolyl) - [1,1' -bis (cyclohexyl))]-4-yl) methyl) -1,3, 2-dioxaborane). The isolated yield was 58%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000242
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.10(d,J＝2.5Hz,4H),2.46–2.36(m,1H),2.32(d,J＝1.5Hz,3H),2.01–1.69(m,7H),1.53–1.36(m,7H),1.26(s,12H),1.17–0.97(m,5H),0.84(d,J＝7.6Hz,1H),0.73(d,J＝7.0Hz,1H). 13 C NMR(101MHz,Chloroform-d)δ144.9,144.9,135.1,128.9,126.6,82.8,44.2,42.9,41.4,39.5,36.1,34.7,34.7,34.5,31.7,30.8,30.4,30.2,25.7,24.8,20.9. 11 B NMR(128MHz,Chloroform-d)δ34.65。
example 56
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (noted DCM, 1mL) and 1-methyl-3- (prop-1-en-1-yl) -1H-indole (noted 1ca, 0.2mmol, 34.2mg) were combined, boron tribromide (0.3mmol, 0.3mL) was added at 0 deg.C, stirred at room temperature under nitrogen (1atm) atmosphere for 12H, triethylamine (noted NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (volume ratio 30:1) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of the structure represented by formula 2ca (white solid, 1-methyl-3- (2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) propyl) -1H-indole). The isolated yield was 50%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000251
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.68–7.62(m,1H),7.29–7.25(m,1H),7.20(ddd,J＝8.2,6.9,1.2Hz,1H),7.08(ddd,J＝8.0,6.8,1.1Hz,1H),6.87(s,1H),3.73(s,3H),2.97(ddd,J＝14.5,7.3,0.9Hz,1H),2.69(ddd,J＝14.5,8.1,0.9Hz,1H),1.49(q,J＝7.5Hz,1H),1.20(d,J＝2.7Hz,12H),1.05(d,J＝7.4Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ136.9,128.3,126.6,121.1,119.4,118.3,115.1,108.8,82.8,32.4,28.0,24.7,24.7,15.6. 11 B NMR(128MHz,Chloroform-d)δ35.10.HRMS(ESI)m/z:[M+H] + calcd forC 18 H 27 BNO 2 + :300.2135；found:300.2136。
example 57
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted DCM, 1mL) and 3- (but-1-en-1-yl) -1-methyl-1H-indole (denoted 1cb, 0.2mmol, 37mg) were combined, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12H, and triethylamine (denoted NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of the structure shown in formula 2cb (1-methyl-3- (2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) butyl) -1H-indole as a colorless oil). The isolated yield was 48%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000252
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.63(dt,J＝7.9,1.0Hz,1H),7.27–7.24(m,1H),7.19(ddd,J＝8.1,6.8,1.2Hz,1H),7.08(ddd,J＝7.9,6.8,1.2Hz,1H),6.87(s,1H),2.90(dd,J＝16.0,8.0Hz,1H),2.77(dd,J＝16.0,8.0Hz,1H),1.56–1.49(m,2H),1.46–1.39(m,1H),1.16(d,J＝8.4Hz,12H),0.97(t,J＝7.4Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ137.0,128.4,126.6,121.3,119.5,118.4,115.3,108.9,83.0,32.6,26.1,24.9,24.8,24.4,13.8. 11 B NMR(128MHz,Chloroform-d)δ34.89.HRMS(ESI)m/z:[M+H] + calcd forC 19 H 29 BNO 2 + :314.2291；found:314.2304。
example 58
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted DCM, 1mL) and 1-methyl-3- (pent-1-en-1-yl) -1H-indole (denoted 1cc, 0.2mmol, 39.8mg) were combined, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 deg.C, stirred at room temperature under nitrogen (1atm) for 12H, and triethylamine (denoted NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a structural compound represented by formula 2cc (colorless oil, 1-methyl-3- (2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) pentyl) -1H-indole). The isolated yield was 57%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000261
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.63(dt,J＝7.9,1.0Hz,1H),7.29–7.23(m,1H),7.19(ddd,J＝8.1,6.8,1.2Hz,1H),7.08(ddd,J＝7.9,6.8,1.2Hz,1H),6.88(s,1H),3.73(s,3H),2.93–2.85(m,1H),2.81–2.74(m,1H),1.53–1.44(m,3H),1.41–1.37(m,2H),1.14(d,J＝9.6Hz,12H),0.91(t,J＝7.1Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ137.0,128.4,126.6,121.3,119.5,118.4,115.4,108.9,82.9,34.0,32.6,31.6,30.3,26.5,24.9,24.7,22.5,14.5. 11 B NMR(128MHz,Chloroform-d)δ35.23.HRMS(ESI)m/z:[M+H] + calcdforC 20 H 31 BNO 2 + :328.2448；found:328.2452。
example 59
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted DCM, 1mL) and 1-methyl-3- (4-phenylbut-1-en-1-yl) -1H-indole (denoted 1cd, 0.2mmol, 52.5mg) were combined at 0 deg.CA solution of boron tribromide in methylene chloride (17% in mass, 0.3mmol, 0.3mL) was added, the mixture was stirred at room temperature for 12 hours under a nitrogen (1atm) atmosphere, and triethylamine (note NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of formula 2cd (colorless oil, 1-methyl-3- (4-phenyl-2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) butyl) -1H-indole). The isolated yield was 53%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000262
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.64(dt,J＝7.9,1.0Hz,1H),7.33–7.26(m,3H),7.24–7.17(m,4H),7.10(ddd,J＝8.0,6.9,1.2Hz,1H),6.86(s,1H),3.73(s,3H),2.97(ddd,J＝14.6,8.5,0.9Hz,1H),2.84(ddd,J＝14.7,7.4,0.9Hz,1H),2.77–2.63(m,2H),1.85(tt,J＝10.0,6.0Hz,2H),1.61–1.56(m,1H),1.19(d,J＝10.3Hz,12H). 13 C NMR(101MHz,Chloroform-d)δ143.1,137.0,128.5,128.4,128.3,126.7,125.6,121.3,119.5,118.4,115.0,108.9,83.1,35.7,33.5,32.6,26.3,24.9,24.8. 11 B NMR(128MHz,Chloroform-d)δ35.44.HRMS(ESI)m/z:[M+H] + calcdforC 25 H 33 BNO 2 + :390.2604；found:390.2607。
example 60
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (as DCM, 1mL) and 1-methyl-3- (pent-2-en-1-yl) -1H-indole (as 1ce, 0.2mmol, 39.8mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) atmosphere for 12H, and triethylamine (as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (designated as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, thenPurifying the product by silica gel column chromatography, and adopting petroleum ether: after elution with ethyl acetate (30: 1 in terms of volume ratio) as an eluent, the solvent was spin-dried under reduced pressure to give the compound represented by formula 2ce (colorless oil, 1-methyl-3- (3- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) pentyl) -1H-indole). The isolated yield was 48% with a linear to branched ratio of 88: 12;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000271
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.63(dt,J＝8.0,1.0Hz,1H),7.25(d,J＝7.2Hz,1H),7.19(ddd,J＝8.1,6.8,1.2Hz,1H),7.07(ddd,J＝8.0,6.9,1.1Hz,1H),6.88(d,J＝1.1Hz,1H),3.72(s,3H),2.96–2.84(m,1H),2.81–2.67(m,1H),1.58–1.43(m,3H),1.29(d,J＝8.2Hz,2H),1.14(d,J＝9.6Hz,12H),0.91(t,J＝7.1Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ137.0,134.7,134.7,129.3,129.1,128.4,126.6,121.3,119.5,118.4,115.4,108.9,82.9,33.9,32.6,25.0,24.9,24.7,22.5,14.5. 11 B NMR(128MHz,Chloroform-d)δ34.43.HRMS(ESI)m/z:[M+H] + calcdforC 20 H 31 BNO 2 + :328.2448；found:328.2449。
example 61
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted DCM, 1mL) and 1-methyl-3- (pent-3-en-1-yl) -1H-indole (denoted 1cf, 0.2mmol, 39.8mg) were combined, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 deg.C, stirred at room temperature under nitrogen (1atm) for 12H, and triethylamine (denoted NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and the product was purified by silica gel column chromatography using petroleum ether: eluting with ethyl acetate (volume ratio of 30:1) as eluent, and spin-drying the solvent under reduced pressure to obtain compound (colorless oily substance, 1-methyl-3- (4- (4,4,5, 5-tetramethyl-1, 3, 2-di-n-butyl) with structure shown in formula 2cfOxaborane-2-yl) pentyl) -1H-indole). Isolated yield 51%, linear to branched ratio 75: 25;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000272
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.64–7.57(m,1H),7.32–7.26(m,1H),7.25–7.14(m,1H),7.09(ddd,J＝8.0,6.9,1.1Hz,1H),6.84(s,1H),3.74(s,3H),2.78–2.71(m,2H),1.80–1.70(m,1H),1.64–1.55(m,11H),1.49–1.43(m,1H),1.25(s,12H),1.12–1.05(m,1H),1.00(d,J＝7.1Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ137.0,134.6,134.5,134.2,134.0,132.8,129.1,129.0,128.0,125.9,121.3,120.6,119.1,118.5,118.3,117.8,115.7,109.0,83.2,82.8,33.3,32.5,29.7,28.9,27.2,25.3,25.0,24.8,24.7,21.8,19.2,18.5,15.5. 11 B NMR(128MHz,Chloroform-d)δ34.83.HRMS(ESI)m/z:[M+H] + calcdforC 20 H 31 BNO 2 + :328.2448；found:328.2446。
example 62
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted DCM, 1mL) and 1-methyl-3- (pent-4-en-1-yl) -1H-indole (denoted 1cg, 0.2mmol, 39.8mg) were combined, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 deg.C, stirred at room temperature under nitrogen (1atm) for 12H, and triethylamine (denoted NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give the compound of the structure represented by formula 2cg (1-methyl-3- (5- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) pentyl) -1H-indole as a colorless oil). The isolated yield was 53%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000281
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.65–7.55(m,1H),7.30–7.25(m,1H),7.20(ddd,J＝8.1,6.9,1.2Hz,1H),7.09(ddd,J＝8.0,6.9,1.1Hz,1H),6.81(s,1H),3.74(s,3H),2.78–2.69(m,2H),1.71(p,J＝7.5Hz,2H),1.52–1.39(m,5H),1.24(s,12H),0.80(t,J＝7.5Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ137.1,134.7,134.7,133.0,129.2,129.1,128.1,126.0,121.4,119.2,118.5,115.8,109.1,82.9,32.6,32.5,30.2,25.1,24.9,24.0. 11 B NMR(128MHz,Chloroform-d)δ34.33.HRMS(ESI)m/z:[M+H] + calcdforC 25 H 33 BNO 2 + :390.2604；found:390.2607.HRMS(ESI)m/z:[M+H] + calcdforC 20 H 31 BNO 2 + :328.2448；found:328.2446。
example 63
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L, dichloromethane (1mL, DCM) and 2-octene (1 ch, 0.2mmol, 22.4mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under a nitrogen (1atm) atmosphere for 12h, triethylamine (NEt, 1) 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of formula 2ch (colorless oil, 2- (pinacolato boronate) -n-octane). The isolated yield was 46% with a linear to branched ratio of 73: 27;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000282
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ1.48–1.35(m,4H),1.28–1.23(m,6H),1.23(d,J＝3.4Hz,12H),1.00–0.93(m,3H),0.89–0.85(m,4H). 13 C NMR(101MHz,Chloroform-d)δ82.9,33.4,32.0,31.2,29.6,29.0,29.0,24.9,24.9,24.8,24.4,22.7,22.7,15.6,14.2,13.8. 11 B NMR(128MHz,Chloroform-d)δ34.45。
example 64
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L, dichloromethane (as DCM, 1mL) and 6-chloro-2-hexene (as 1ci, 0.2mmol, 23.6mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) atmosphere for 12h, triethylamine (as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (volume ratio 30:1) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of formula 2ci (colorless oil, 2- (pinacolboronic acid ester) -6-chlorohexane). The isolated yield was 51% with a linear to branched ratio of 76: 24;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000291
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ3.59–3.34(m,2H),2.02–1.71(m,2H),1.54–1.37(m,5H),1.23(d,J＝3.0Hz,12H),1.01–0.85(m,3H). 13 C NMR(101MHz,Chloroform-d)δ83.1,83.0,45.5,45.3,34.3,33.0,32.7,32.5,32.4,29.7,28.4,26.3,25.0,24.90,24.86,24.2,15.6,13.7. 11 B NMR(128MHz,Chloroform-d)δ34.24。
example 65
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted DCM, 1mL) and cyclohexene (denoted 1cj, 0.2mmol, 16.4mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃ and the mixture was placed in a chamber under nitrogen (1atm) atmosphereStirred for 12h, added triethylamine (noted as NEt) 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give the compound of formula 2cj (colorless oil, 1- (pinacolboronic acid ester) cyclohexane). The isolated yield was 44%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000292
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ1.68–1.55(m,4H),1.40–1.26(m,6H),1.22(s,12H),1.02–0.92(m,1H). 13 C NMR(101MHz,Chloroform-d)δ82.8,28.1,27.2,26.9,24.8. 11 B NMR(128MHz,Chloroform-d)δ34.36。
example 66
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted DCM, 1mL) and cycloheptene (denoted 1ck, 0.2mmol, 20.2mg) were combined, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 deg.C, stirring was carried out at room temperature under a nitrogen (1atm) atmosphere for 12h, and triethylamine (denoted NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of the formula 2ck (colorless oil, 1- (pinacolboronic acid ester) cycloheptane). The isolated yield was 44%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000301
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ1.79–1.61(m,5H),1.54–1.40(m,7H),1.23(s,12H),1.07(s,1H). 13 C NMR(101MHz,Chloroform-d)δ82.9,29.8,29.1,28.5,24.9. 11 B NMR(128MHz,Chloroform-d)δ34.76。
example 67
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 1,1-2, 2-tetramethylethylene (denoted as 1cl, 0.2mmol, 16.8mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under a nitrogen (1atm) atmosphere for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 by volume) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of formula 2cl (colorless oil, 2- (pinacolboronic acid ester) -2-methyl-3-methyl-butane). The isolated yield was 59%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000302
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ1.65–1.58(m,1H),1.23(s,12H),0.86(s,6H),0.85(s,3H),0.84(s,3H). 13 C NMR(101MHz,Chloroform-d)δ82.7,34.6,24.7,21.3,18.4. 11 B NMR(128MHz,Chloroform-d)δ35.13。
example 68
Diisopropylethylamine (as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 4-octene (denoted as 1cm, 0.2mmol, 22.4mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (designated as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h and then chromatographed on silica gel columnPurifying the product by adopting petroleum ether: after elution with ethyl acetate (volume ratio 30:1) as an eluent, the solvent was spin-dried under reduced pressure to give a compound of the structure shown by formula 2cm (colorless oil, 4- (pinacolboronic acid ester) n-octane). The isolated yield was 58%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000311
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ1.43–1.25(m,11H),1.23(s,12H),0.98–0.92(m,1H),0.87(td,J＝7.0,3.1Hz,6H). 13 C NMR(101MHz,Chloroform-d)δ82.8,33.9,31.7,31.2,24.9,23.1,22.5,14.5,14.2. 11 B NMR(128MHz,Chloroform-d)δ34.37。
example 69
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and 1, 6-diphenyl-3-hexene (denoted as 1cn, 0.2mmol, 47.2mg) were combined, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 deg.C, stirred at room temperature under nitrogen (1atm) atmosphere for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after ethyl acetate (volume ratio of 30:1) was used as an eluent for elution, the solvent was spin-dried under reduced pressure to give a compound having a structure represented by formula 2cn (colorless oil, 1, 6-diphenyl-3- (pinacolboronic acid ester) n-hexane). The isolated yield was 40%;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000312
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ7.31–7.24(m,4H),7.23–7.13(m,6H),2.70–2.53(m,4H),1.86–1.60(m,4H),1.55–1.41(m,2H),1.27(s,12H),1.14–1.06(m,1H). 13 C NMR(101MHz,Chloroform-d)δ143.0,142.8,128.4,128.3,128.2,128.2,82.9,36.2,35.6,33.3,30.9,30.9,24.8,24.8. 11 B NMR(128MHz,Chloroform-d)δ35.40.HRMS(ESI)m/z:[M+H] + calcdforC 24 H 34 BO 2 + :365.2652；found:365.2662。
example 70
Diisopropylethylamine (note as i Pr 2 NEt, 0.6mmol, 99. mu.L), dichloromethane (denoted as DCM, 1mL) and α -thujene (denoted as 1co, 0.2mmol, 40.8mg) were mixed, a solution of boron tribromide in dichloromethane (17% by mass, 0.3mmol, 0.3mL) was added at 0 ℃, stirred at room temperature under nitrogen (1atm) for 12h, and triethylamine (denoted as NEt) was added 3 0.6mmol, 84. mu.L) and pinacol (noted as pinacol, 0.3mmol, 35.4mg) were stirred at room temperature for 1h, and then the product was purified by silica gel column chromatography using petroleum ether: after elution with ethyl acetate (30: 1 in terms of volume ratio) aS an eluent, the solvent was spin-dried under reduced pressure to give a compound represented by the formula 2co (colorless oil, 4,4,5, 5-tetramethyl-2- ((3R, 3aS, 7S, 8aS) -3,5,8, 8-tetramethyloctahydro-1H-3 a, 7-azaazepin-6-yl) -1,3, 2-dioxaborane). The isolated yield was 62% with a linear to branched ratio of 98: 2;
the chemical reaction formula of the preparation process is as follows:
Figure BDA0002728382220000313
the characterization data are: 1 H NMR(400MHz,Chloroform-d)δ1.83(dq,J＝11.9,5.9Hz,1H),1.77–1.71(m,3H),1.64–1.58(m,2H),1.51–1.32(m,6H),1.24(d,J＝5.3Hz,12H),1.21–1.17(m,1H),1.13(s,3H),1.02(d,J＝7.3Hz,3H),0.92(s,3H),0.82(d,J＝7.1Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ82.9,58.0,56.4,54.5,47.5,44.2,42.6,39.4,37.2,35.5,29.2,27.2,25.7,25.0,24.7,21.8,15.5. 11 B NMR(128MHz,Chloroform-d)δ34.26。
the foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.

Claims (7)

1. A preparation method of a saturated monoboron compound is characterized by comprising the following steps:
mixing an olefin compound, an alkali compound, a boron halide compound and an organic solvent, carrying out a boronation reaction, adding triethylamine and pinacol or adding triethylamine and 1,8-diaminonaphthalene, and carrying out an esterification reaction to obtain a saturated monoboron compound;
the alkali compound is diisopropylethylamine or diisopropylamine;
the boronization reaction is carried out in a protective atmosphere;
the protective atmosphere is nitrogen atmosphere or argon atmosphere.
2. The method according to claim 1, wherein the molar ratio of the olefinic compound, the basic compound and the boron halide compound is 1: (1-6): (1-6).
3. The process according to claim 1 or 2, wherein the olefinic compound has a structure represented by formula 1 or formula 2:
Figure 97729DEST_PATH_IMAGE002
in the formula 1, the compound is shown in the specification,
Figure 47493DEST_PATH_IMAGE004
formula 2;
wherein R is 2 、R 3 And R 4 Independently aryl, alkyl or hydrogen;
the R is 1 Beta-naphthalene, ferrocene, N-methylindole, phenyl, substituted phenyl or alkyl;
the substituent in the substituted phenyl is methyl, fluorine, chlorine, bromine, tertiary butyl, phenyl, trifluoromethyl, pentafluorophenyl or methylthio.
4. The method according to claim 1, wherein the molar ratio of the olefinic compound to triethylamine is 1: 3;
the molar ratio of the olefin compound to the pinacol is 1: 1.5;
the molar ratio of the olefin compound to the 1,8-diaminonaphthalene is 1: 1.5.
5. The production method according to claim 1 or 2, wherein the boron halide compound is boron tribromide, boron trichloride, or boron dimethyl sulfide complex tribromide.
6. The method of claim 1, wherein the organic solvent is toluene, dichloromethane, 1, 2-dichloroethane, or n-hexane.
7. The preparation method according to claim 1, wherein the temperature of the boronation reaction is 20 to 80 ℃, and the time of the boronation reaction is 1 to 24 hours.
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