CN115710287B - Ring-opening boronation reaction method for cyclopropane compound under no metal catalysis - Google Patents

Ring-opening boronation reaction method for cyclopropane compound under no metal catalysis Download PDF

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CN115710287B
CN115710287B CN202211518968.4A CN202211518968A CN115710287B CN 115710287 B CN115710287 B CN 115710287B CN 202211518968 A CN202211518968 A CN 202211518968A CN 115710287 B CN115710287 B CN 115710287B
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CN115710287A (en
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吴立朋
李思达
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

The invention relates to a reaction method for ring-opening boration of cyclopropane compounds under metal-free catalysis, which is characterized in that the method comprises the steps of mixing and heating the cyclopropane compounds, the naphthol borane and an organic solvent in a protective atmosphere for carrying out boration reaction, and stirring the mixture for 1 hour at room temperature by triethylamine and pinacol to obtain the boron-containing compounds. The invention has low production cost, simple and convenient operation of reaction conditions, is suitable for industrial production, and the synthesized saturated boric acid ester compound has good chemical selectivity and high functional group tolerance, and is beneficial to separation and purification of products.

Description

Ring-opening boronation reaction method for cyclopropane compound under no metal catalysis
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a reaction method for ring-opening boronation of cyclopropane compounds under metal-free catalysis.
Background
The cyclopropane structure of the cyclopropane compound has great and potential utilization value in medicament derivation and modification, and a plurality of scientists are attracted in recent years to conduct modification exploration on the cyclopropane compound, wherein the realization of activation and cleavage of carbon-carbon bonds of the cyclopropane compound to obtain corresponding functional structure products is a big research hotspot in a short period of time.
Although great progress is made in the carbon-carbon bond activation of the cyclopropane compounds catalyzed by the transition metals, noble metals such as rhodium, iridium and the like, organic phosphine and nitrogen ligands are generally used in the transition metal catalytic reaction system, so that the reaction cost and the post-treatment cost are increased, the problems of metal residual pollution in different degrees can be generated in the noble metal catalytic reaction system, the atomic economy is poor, the environment is not protected, the hydrocarbon bond activated product and the product with different carbon-carbon bond broken in the reaction generally exist, the chemical selectivity and the position selectivity are also challenged, and therefore, a reaction system with lower reaction cost needs to be developed to cope with the problems.
Disclosure of Invention
The invention aims to solve the technical problem of providing a reaction method for ring-opening boronation of cyclopropane compounds under metal catalysis with low cost and convenient operation.
In order to solve the problems, the reaction method for ring-opening boronation of cyclopropane compounds under metal-free catalysis is characterized by comprising the following steps: the method is characterized in that cyclopropane compounds, naphthol borane and an organic solvent are mixed and heated in a protective atmosphere to carry out a boration reaction, and then triethylamine and pinacol are stirred for 1 hour at room temperature to obtain the boron-containing compounds.
The molar ratio of the cyclopropane compound to the naphthol borane to the pinacol is 1: (1.2 to 3.0): (1.2-3.0); the molar ratio of the triethylamine to the pinacol is 1:1.
the structural formula of the cyclopropane compound is shown as follows:
；
wherein: r is R 1 Is one of aryl, aromatic heterocycle or alkyl, R 2 And R is 3 Independently is one of aryl, alkyl or hydrogen, and X is oxygen or sulfur.
R 1 Is one of beta-naphthalene, aromatic heterocycle, phenyl, substituted phenyl or alkyl; the R is 2 Is one of phenyl, alkyl or hydrogen; the R is 3 Is one of phenyl, substituted phenyl or hydrogen; the substituent in the substituted phenyl is one of methyl, fluorine, chlorine, bromine, tertiary butyl, phenyl, trifluoromethyl, cyano, ester, N-dimethyl, acetyl, nitro or methoxy.
The organic solvent is one of toluene, tetrahydrofuran, paraxylene, 1, 4-dioxane, 1, 2-dichloroethane, diethylene glycol dimethyl ether or methyl tertiary butyl ether.
The condition of the boration reaction is that the temperature is 100-150 ℃ and the time is 6-48 h.
The protective atmosphere is nitrogen atmosphere or argon atmosphere.
Compared with the prior art, the invention has the following advantages:
1. According to the invention, the saturated straight-chain ring-opening monoboron compound of cyclopropane is prepared by mixing and heating infantile naphthol borane and cyclopropane compound under the condition of no metal catalysis to realize the carbon-carbon bond activation ring-opening selective boration reaction.
2. According to the invention, only the naphthol borane is used as the boration reagent, transition metal catalysis is not needed, the economy of the reaction is improved, the atom economy is good, and the requirements of green chemistry are met.
3. The invention has the advantages of cheap and easily obtained raw materials, low production cost, simple and convenient operation of reaction conditions and suitability for industrial production.
4. The saturated boric acid ester compound synthesized by the invention has good chemical selectivity and high functional group tolerance, and is beneficial to separation and purification of products.
Detailed Description
The method is characterized in that the cyclopropane compound, the infantile naphthol borane and the organic solvent are mixed and heated in a protective atmosphere to carry out the boration reaction; and then stirring the mixture for 1 hour at room temperature by triethylamine and pinacol to obtain the boron-containing compound.
The reaction equation is as follows:
wherein: the molar ratio of the cyclopropane compound to the naphthol borane to the pinacol is 1: (1.2 to 3.0): (1.2 to 3.0).
The molar ratio of cyclopropane compound to naphthol borane is preferably 1: (1.5 to 3.0), most preferably 1: (1.7-2.5).
The molar ratio of triethylamine to pinacol was 1:1.
in the present invention, the volume ratio of the molar amount of the cyclopropane compound to the organic solvent is preferably (0.2 to 0.3) mmol: (0.5-3) mL.
The structural formula of the cyclopropane compound is shown as follows:
；
wherein: r is R 1 Is one of aryl, aromatic heterocycle or alkyl, R 2 And R is 3 Independently is one of aryl, alkyl or hydrogen, and X is oxygen or sulfur.
Preferably: r is R 1 Is one of beta-naphthalene, aromatic heterocycle, phenyl, substituted phenyl or alkyl; r is R 2 Is one of phenyl, alkyl or hydrogen; r is R 3 Is phenyl, substituted phenylOr hydrogen; the substituent in the substituted phenyl is one of methyl, fluorine, chlorine, bromine, tertiary butyl, phenyl, trifluoromethyl, cyano, ester, N-dimethyl, acetyl, nitro or methoxy. The substitution site of the substituent is not particularly limited in the present invention.
In particular embodiments of the invention, the cyclopropane compound is N-cyclopropyl-4-methylbenzamide, N-cyclopropyl-4-tert-butylbenzamide, N-cyclopropyl-4-methoxybenzamide, N-cyclopropyl-4-phenylbenzamide, N-cyclopropyl-4-N, N-dimethylbenzamide, N-cyclopropyl-4-fluorobenzamide, N-cyclopropyl-4-chlorobenzamide, N-cyclopropyl-4-bromobenzamide, N-cyclopropyl-4-trifluoromethylbenzamide, N-cyclopropyl-4-acetylbenzamide, N-cyclopropyl-4-methanoylbenzamide, N-cyclopropyl-4-nitrobenzamide, N-cyclopropyl-4-cyanobenzamide, N-cyclopropyl-beta-naphthamide, N-cyclopropyl-pentafluorobenzamide, N-cyclopropyl-4-diphenylphosphinobenzamide, N-cyclopropyl-2-methylbenzamide, N-cyclopropyl-2-chlorobenzamide, N-cyclopropyl-4-methylbenzamide, N-cyclopropyl-4-nitrobenzamide, N-cyclopropyl-4-cyanobenzamide, N-cyclopropyl-2-chlorobenzoamide, N-cyclopropyl-4-nitrobenzamide, N-cyclopropyl-4-cyanobenzamide, N-cyclopropylamide, N-2-cyclopropylbenzamide N-cyclopropyl-2-ferrocenecarboxamide, N- (1-methylcyclopropyl) -benzamide, N- (1-phenylcyclopropyl) -benzamide, N- (1- (2-cyclopentenyl) cyclopropyl) -benzamide, N- (1-methylcyclopropyl) -benzamide, N- (2-phenylcyclopropyl) -benzamide, N- (2- (3, 4-difluorophenyl) cyclopropyl) -benzamide, N-cyclopropyl-1-methylcyclohexyl-1-carboxamide, N-cyclopropyl-1-adamantylcarboxamide, N-cyclopropyl-1-cyclohexenyl-1-carboxamide, N-cyclopropyl-pivaloamide, N- (1- (2-cyclopentenyl) cyclopropyl) -pivaloamide, N-cyclopropyl-thio-pivaloamide or N-cyclopropyl-thio-benzamide.
The organic solvent is one of toluene, tetrahydrofuran, paraxylene, 1, 4-dioxane, 1, 2-dichloroethane, diethylene glycol dimethyl ether or methyl tertiary butyl ether. Preferably: toluene, tetrahydrofuran, para-xylene, 1, 4-dioxane or diethylene glycol dimethyl ether.
In the present invention, the mixing is preferably to mix the cyclopropane compound, the naphthol borane and the organic solvent and then heat them, cool them to room temperature after the reaction is completed, add triethylamine and pinacol in an inert gas atmosphere, and then stir them at room temperature for one hour. The method for adding the cyclopropane compound, the naphthol borane and the organic solvent is not particularly limited, and the method is well known to those skilled in the art.
In the present invention, the protective atmosphere is a nitrogen atmosphere or an argon atmosphere. The pressure of the protective atmosphere is preferably 1atm; the temperature of the boration reaction is preferably 100-150 ℃, the time of the boration reaction is preferably 6-48 h, more preferably 10-36 h, and most preferably 12-24 h. In the present invention, the boration reaction is preferably carried out under stirring conditions, and the stirring conditions are not particularly limited in the present invention, and may be carried out by a process well known to those skilled in the art.
After the completion of the boration reaction, the present invention also preferably includes separation, and the present invention is not limited to any particular one, and the separation may be performed by using column chromatography and spin drying under reduced pressure, which are well known to those skilled in the art. In the examples of the present invention, the product system containing the saturated mono-boron compound was directly obtained without separation in examples 1 to 19, and the yield of the saturated mono-boron compound in the product system was detected by gas phase. If the product system is required to be separated and purified, the separation method is referred to above.
In the present invention, all raw materials are commercially available products well known to those skilled in the art unless specified otherwise.
Example 1
Infantile naphthol borane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (1 mL) and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 140℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 83%.
The chemical reaction formula of the preparation process is as follows:
。
example 2
Infantile naphthol borane (designated as HBcat,0.4mmol, 42.7. Mu.L), tetrahydrofuran (1 mL) and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 140℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 61%.
The chemical reaction formula of the preparation process is as follows:
。
example 3
Infantile naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), 1, 4-dioxane (1 mL) and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 140℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 82%.
The chemical reaction formula of the preparation process is as follows:
。
example 4
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), paraxylene (1 mL) and N-cyclopropylbenzamide (designated 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 140℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 71%.
The chemical reaction formula of the preparation process is as follows:
。
example 5
Child naphthol borane (recorded as HBcat,0.4mmol, 42.7. Mu.L), methyl tert-butyl ether (1 mL) and N-cyclopropyl benzamide (recorded as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 140℃for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 11%.
The chemical reaction formula of the preparation process is as follows:
。
example 6
Child naphthol borane (recorded as HBcat,0.4mmol, 42.7. Mu.L), diethylene glycol dimethyl ether (1 mL) and N-cyclopropyl benzamide (recorded as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 140℃for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 64%.
The chemical reaction formula of the preparation process is as follows:
。
example 7
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), 1, 2-dichloroethane (1 mL) and N-cyclopropylbenzamide (designated 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 140℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 83%.
The chemical reaction formula of the preparation process is as follows:
。
example 8
Infantile naphthol borane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 140℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 95%.
The chemical reaction formula of the preparation process is as follows:
。
example 9
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (0.5 mL) and N-cyclopropylbenzamide (designated 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 140℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 38%.
The chemical reaction formula of the preparation process is as follows:
。
example 10
Infantile naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), 1, 4-dioxane (2 mL) and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 140℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 91%.
The chemical reaction formula of the preparation process is as follows:
。
example 11
Infantile naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), 1, 4-dioxane (0.5 mL) and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 140℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added thereto and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 39%.
The chemical reaction formula of the preparation process is as follows:
。
example 12
Infantile naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), 1, 4-dioxane (2 mL) and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added thereto and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 91%.
The chemical reaction formula of the preparation process is as follows:
。
example 13
Infantile naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), 1, 4-dioxane (2 mL) and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 100℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added thereto and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 70%.
The chemical reaction formula of the preparation process is as follows:
。
example 14
Infantile naphthol borane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 95%.
The chemical reaction formula of the preparation process is as follows:
。
example 15
Infantile naphthol borane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 100℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 72%.
The chemical reaction formula of the preparation process is as follows:
。
example 16
Infantile naphthol borane (designated as HBcat,0.24mmol, 25.6. Mu.L), toluene (2 mL) and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere and stirred at 120℃for 12 hours, after which triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 78%.
The chemical reaction formula of the preparation process is as follows:
。
example 17
Infantile naphthol borane (designated as HBcat,0.3mmol, 32.0. Mu.L), toluene (2 mL) and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 86%.
The chemical reaction formula of the preparation process is as follows:
。
example 18
Infantile naphthol borane (designated as HBcat,0.35mmol, 37.3. Mu.L), toluene (2 mL) and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere and stirred at 120℃for 12 hours, after which triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 95%.
The chemical reaction formula of the preparation process is as follows:
。
example 19
Infantile naphthol borane (designated as HBcat,0.6mmol, 64.1. Mu.L), toluene (2 mL) and N-cyclopropylbenzamide (designated as 1a,0.2mmol,32.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 a. The GC detection yield was 65%.
The chemical reaction formula of the preparation process is as follows:
。
the N- (3-pinacol borate propyl) benzamide compounds prepared in examples 1-19 and having the structure shown in formula 2a are all yellow liquids, and the characterization data are all: 1 H NMR (400 MHz, Chloroform-d) δ 7.80 – 7.74 (m, 2H), 7.50 – 7.45 (m, 1H), 7.44 – 7.38 (m, 2H), 6.48 (s, 1H), 3.44 (td, J= 6.9, 5.5 Hz, 2H), 1.74 (p, J = 7.2 Hz, 2H), 1.22 (s, 12H), 0.89 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.7, 135.1, 131.3, 128.5, 127.0, 83.5, 42.3, 24.9, 23.7. 11 B NMR (128 MHz, Chloroform-d) δ 34.36。
example 20
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-4-methylbenzamide (designated 1b,0.2mmol,35.0 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 b. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a structural compound represented by formula 2b as a white solid with a separation yield of 77%.
The chemical reaction formula of the preparation process is as follows:
；
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.66 (d, J = 8.1 Hz, 2H), 7.20 (d, J = 7.9 Hz, 2H), 6.43 (s, 1H), 3.43 (td, J = 6.9, 5.4 Hz, 2H), 2.38 (s, 3H), 1.73 (p, J = 7.1 Hz, 2H), 1.23 (s, 12H), 0.88 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.6, 141.6, 132.2, 129.2, 127.0, 83.4, 42.2, 24.9, 23.8, 21.5. 11 B NMR (128 MHz, Chloroform-d) δ 34.41。
example 21
Infantile naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-4-t-butylbenzamide (designated as 1c,0.2mmol,43.4 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 c. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a compound of formula 2c as a white solid with a separation yield of 46%.
The chemical reaction formula of the preparation process is as follows:
；
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.72 – 7.66 (m, 2H), 7.45 – 7.38 (m, 2H), 6.43 (s, 1H), 3.43 (td, J = 6.9, 5.5 Hz, 2H), 1.72 (p, J = 7.3 Hz, 2H), 1.32 (s, 9H), 1.22 (s, 12H), 0.87 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.6, 154.7, 132.2, 126.8, 125.4, 83.4, 42.1, 34.9, 31.3, 24.9, 23.8. 11 B NMR (128 MHz, Chloroform-d) δ 34.25。
example 22
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-4-methoxybenzamide (designated 1d,0.2mmol,38.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 d. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as eluent, the solvent was dried under reduced pressure to give the structural compound represented by formula 2d as a white solid with a separation yield of 75%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.77 – 7.69 (m, 2H), 6.94 – 6.86 (m, 2H), 6.38 (s, 1H), 3.84 (s, 3H), 3.42 (td, J = 6.9, 5.4 Hz, 2H), 1.79 – 1.68 (m, 2H), 1.23 (s, 12H), 0.88 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.2, 162.1, 128.8, 127.4, 113.7, 83.4, 55.5, 42.2, 24.9, 23.8. 11 B NMR (128 MHz, Chloroform-d) δ 34.06。
example 23
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-4-phenylbenzamide (designated 1e,0.2mmol,47.4 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 e. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as eluent, the solvent was dried under reduced pressure to give the structural compound represented by formula 2e as a white solid with a separation yield of 50%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.87 – 7.81 (m, 2H), 7.66 – 7.51 (m, 4H), 7.49 – 7.42 (m, 2H), 7.40 – 7.34 (m, 1H), 6.61 (t, J = 5.5 Hz, 1H), 3.46 (td, J = 6.9, 5.4 Hz, 2H), 1.76 (p, J = 7.2 Hz, 2H), 1.23 (s, 12H), 0.90 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.3, 144.1, 140.2, 133.7, 128.9, 128.0, 127.5, 127.2, 127.2, 83.4, 42.3, 24.9, 23.7. 11 B NMR (128 MHz, Chloroform-d) δ 34.23。
example 24
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-4-N, N-dimethylbenzamide (designated 1f,0.2mmol,40.8 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 f. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a compound of formula 2f as a white solid with a separation yield of 60%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.70 – 7.62 (m, 2H), 6.69 – 6.61 (m, 2H), 6.24 (s, 1H), 3.41 (td, J = 7.0, 5.5 Hz, 2H), 3.00 (s, 6H), 1.78 – 1.70 (m, 2H), 1.24 (s, 12H), 0.87 (t, J = 7.7 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.4, 152.3, 128.3, 121.8, 111.0, 83.2, 41.9, 40.1, 24.8, 23.8. 11 B NMR (128 MHz, Chloroform-d) δ 33.98。
example 25
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-4-fluorobenzamide (designated 1g,0.2mmol,35.8 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 g. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to give a compound of the formula 2g as a white solid with a separation yield of 60%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.81 – 7.73 (m, 2H), 7.11 – 7.03 (m, 2H), 6.53 (s, 1H), 3.41 (td, J = 6.8, 5.4 Hz, 2H), 1.72 (p, J = 7.2 Hz, 2H), 1.21 (s, 12H), 0.87 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.6, 165.9, 163.4, 131.3, 131.2, 129.3, 129.2, 115.6, 115.4, 83.4, 42.3, 24.9, 23.6. 11 B NMR (128 MHz, Chloroform-d) δ 34.15. 19 F NMR (376 MHz, Chloroform-d) δ -108.82 (ddd, J = 13.7, 8.5, 5.2 Hz)。
example 26
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-4-chlorobenzamide (designated 1h,0.2mmol,39.0 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to give a product system containing the structural compound represented by formula 2 h. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a compound of the structure shown in formula 2h as a white solid with a separation yield of 46%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.74 – 7.64 (m, 2H), 7.42 – 7.31 (m, 2H), 6.50 (s, 1H), 3.43 (td, J = 6.8, 5.4 Hz, 2H), 1.74 (p, J = 7.3 Hz, 2H), 1.23 (s, 12H), 0.88 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.5, 137.5, 133.5, 128.8, 128.5, 83.5, 42.3, 24.9, 23.6. 11 B NMR (128 MHz, Chloroform-d) δ 34.43。
example 27
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-4-bromobenzamide (designated 1i,0.2mmol,47.8 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 i. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as eluent, the solvent was dried under reduced pressure to give the structural compound represented by formula 2i as a white solid with a separation yield of 75%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.66 – 7.60 (m, 2H), 7.56 – 7.49 (m, 2H), 6.60 (t, J = 5.5 Hz, 1H), 3.41 (td, J = 6.9, 5.4 Hz, 2H), 1.72 (p, J = 7.2 Hz, 2H), 1.21 (s, 12H), 0.87 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.6, 133.8, 131.7, 128.7, 125.9, 83.4, 42.3, 24.9, 23.5. 11 B NMR (128 MHz, Chloroform-d) δ 33.63。
example 28
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-4-trifluoromethylbenzamide (designated 1j,0.2mmol,45.8 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 j. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a compound of the formula 2j as a white solid with a separation yield of 50%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.87 (d, J = 7.8 Hz, 2H), 7.66 (d, J = 8.1 Hz, 2H), 6.70 (s, 1H), 3.44 (td, J = 6.8, 5.4 Hz, 2H), 1.74 (p, J = 7.2 Hz, 2H), 1.21 (s, 12H), 0.88 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.4, 138.4, 133.2, 132.9, 127.5, 125.5 (q, J = 3.8 Hz), 83.5, 42.4, 24.8, 23.5. 11 B NMR (128 MHz, Chloroform-d) δ 34.09. 19 F NMR (376 MHz, Chloroform-d) δ -62.92。
example 29
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-4-acetylbenzamide (designated 1k,0.2mmol,40.6 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 k. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 8:1) as an eluent, the solvent was dried under reduced pressure to obtain a compound of the formula 2k as a colorless liquid with a separation yield of 35%.
The chemical reaction formula of the preparation process is as follows:
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the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 8.03 – 7.96 (m, 2H), 7.89 – 7.78 (m, 2H), 6.61 (s, 1H), 3.46 (td, J = 6.8, 5.4 Hz, 2H), 2.63 (s, 3H), 1.76 (p, J = 7.2 Hz, 2H), 1.23 (s, 12H), 0.93 – 0.88 (m, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 197.6, 166.6, 139.1, 139.0, 128.5, 127.4, 83.5, 42.4, 26.9, 24.9, 23.5. 11 B NMR (128 MHz, Chloroform-d) δ 34.01。
example 30
Infantile naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-4-methanoylbenzamide (designated as 1L,0.2mmol,43.8 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2L. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to give a compound of formula 2l as a white solid with a separation yield of 73%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 8.13 – 7.99 (m, 2H), 7.84 – 7.77 (m, 2H), 6.77 (s, 1H), 3.91 (s, 3H), 3.42 (td, J = 6.8, 5.4 Hz, 2H), 1.72 (p, J = 7.2 Hz, 2H), 1.19 (s, 12H), 0.87 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.7, 166.4, 139.0, 132.5, 129.7, 127.1, 83.4, 52.4, 42.4, 24.8, 23.5. 11 B NMR (128 MHz, Chloroform-d) δ 33.57。
example 31
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-4-nitrobenzamide (designated 1m,0.2mmol,41.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 m. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 10:1) as an eluent, the solvent was dried under reduced pressure to give a compound of formula 2m as a white solid with a separation yield of 64%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 8.29 – 8.22 (m, 2H), 7.97 – 7.90 (m, 2H), 6.82 (s, 1H), 3.45 (td, J = 6.8, 5.4 Hz, 2H), 1.75 (p, J = 7.1 Hz, 2H), 1.22 (s, 12H), 0.89 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 165.5, 149.5, 140.7, 128.2, 123.8, 83.5, 42.6, 24.9, 23.4. 11 B NMR (128 MHz, Chloroform-d) δ 34.18。
example 32
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-4-cyanobenzamide (designated 1N,0.2mmol,39.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2N. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a compound of formula 2n as a white solid with a separation yield of 50%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.92 – 7.81 (m, 2H), 7.76 – 7.69 (m, 2H), 6.72 (s, 1H), 3.46 (td, J = 6.8, 5.4 Hz, 2H), 1.75 (q, J = 7.1 Hz, 2H), 1.23 (s, 12H), 0.90 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 165.8, 139.0, 132.4, 127.8, 118.2, 114.9, 83.5, 42.5, 24.9, 23.4. 11 B NMR (128 MHz, Chloroform-d) δ 34.39。
example 33
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-. Beta. -naphthalenecarboxamide (designated 1o,0.2mmol,42.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 o. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to give a compound of formula 2o as a white solid with a separation yield of 46%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 8.28 (s, 1H), 7.87 (ddt, J = 13.4, 10.3, 6.6 Hz, 4H), 7.60 – 7.48 (m, 2H), 6.63 (s, 1H), 3.51 (td, J = 6.9, 5.4 Hz, 2H), 1.79 (p, J = 7.2 Hz, 2H), 1.23 (s, 12H), 0.93 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.7, 134.8, 132.8, 132.4, 128.4, 127.8, 127.6, 127.4, 126.8, 123.8, 83.4, 42.4, 24.9, 23.8. 11 B NMR (128 MHz, Chloroform-d) δ 34.48。
example 34
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-pentafluorobenzamide (designated 1p,0.2mmol,50.0 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 p. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a compound of formula 2p as a colorless liquid, with a separation yield of 44%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 6.46 (s, 1H), 3.38 (td, J= 6.8, 5.5 Hz, 2H), 1.70 – 1.61 (m, 2H), 1.15 (s, 12H), 0.81 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 157.1, 145.3, 119.5, 118.6, 117.0, 83.4, 42.4, 24.7, 23.1. 11 B NMR (128 MHz, Chloroform-d) δ 33.95. 19 F NMR (376 MHz, Chloroform-d) δ -140.28 – -140.52 (m), -151.30 (tt, J = 20.7, 3.0 Hz), -160.12 – -160.48 (m)。
example 35
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-4-diphenylphosphinobenzamide (designated 1q,0.2mmol,69.0 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 q. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a compound of the formula 2q as a colorless liquid with a separation yield of 45%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.74 – 7.67 (m, 2H), 7.40 – 7.25 (m, 12H), 6.47 (s, 1H), 3.44 (td, J = 6.9, 5.5 Hz, 2H), 1.73 (p, J = 7.2 Hz, 2H), 1.21 (s, 12H), 0.89 – 0.85 (m, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.4, 141.7, 136.6, 136.5, 135.2, 134.0, 133.8, 133.7, 133.5, 129.1, 128.8, 128.7, 126.9, 126.9, 83.4, 42.3, 24.9, 23.7. 11 B NMR (128 MHz, Chloroform-d) δ 34.48. 31 P NMR (162 MHz, Chloroform-d) δ -5.61。
example 36
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-2-methylbenzamide (designated 1r,0.2mmol,35.0 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 150℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 r. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a compound of the formula 2r as a colorless liquid, with a separation yield of 18%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.38 – 7.26 (m, 2H), 7.21 – 7.09 (m, 2H), 6.12 (s, 1H), 3.43 (td, J = 6.8, 5.5 Hz, 2H), 2.44 (s, 3H), 1.73 (p, J = 7.2 Hz, 2H), 1.19 (s, 12H), 0.88 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 170.1, 136.9, 135.9, 130.8, 129.6, 126.6, 125.6, 83.3, 41.9, 24.7, 23.6, 19.7. 11 B NMR (128 MHz, Chloroform-d) δ 34.28。
example 37
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-2-chlorobenzamide (designated 1s,0.2mmol,39.0 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 150℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 s. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a compound of the formula 2s as a colorless liquid, with a separation yield of 28%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.65 – 7.56 (m, 1H), 7.45 – 7.24 (m, 3H), 6.47 (s, 1H), 3.45 (td, J = 6.9, 5.5 Hz, 2H), 1.74 (p, J = 7.2 Hz, 2H), 1.19 (s, 12H), 0.88 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.6, 135.8, 131.1, 130.7, 130.2, 130.1, 127.1, 83.4, 42.3, 24.8, 23.6. 11 B NMR (128 MHz, Chloroform-d) δ 34.13。
example 38
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-3-methylbenzamide (designated 1t,0.2mmol,35.0 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 t. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to give a compound of formula 2t as a white solid with a separation yield of 73%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.58 (s, 1H), 7.52 (dq, J= 5.7, 1.9 Hz, 1H), 7.33 – 7.24 (m, 2H), 6.43 (s, 1H), 3.43 (td, J = 6.9, 5.5 Hz, 2H), 2.38 (s, 3H), 1.73 (p, J = 7.7, 7.3 Hz, 3H), 1.22 (s, 12H), 0.88 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.8, 138.2, 135.0, 131.9, 128.2, 127.6, 123.8, 83.3, 42.1, 24.7, 23.6, 21.3. 11 B NMR (128 MHz, Chloroform-d) δ 34.04。
example 39
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-3-chlorobenzamide (designated 1u,0.2mmol,39.0 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 u. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to give a compound of formula 2u as a white solid with a separation yield of 59%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.73 (t, J = 1.9 Hz, 1H), 7.63 (dt, J = 7.6, 1.4 Hz, 1H), 7.43 (ddd, J = 8.0, 2.1, 1.1 Hz, 1H), 7.33 (t, J = 7.9 Hz, 1H), 6.63 (s, 1H), 3.42 (td, J = 6.8, 5.4 Hz, 2H), 1.73 (p, J= 7.2 Hz, 2H), 1.21 (s, 12H), 0.87 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.3, 137.0, 134.7, 131.3, 129.8, 127.3, 125.2, 83.5, 42.4, 24.9, 23.5. 11 B NMR (128 MHz, Chloroform-d) δ 34.09。
example 40
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-2-furancarboxamide (designated 1v,0.2mmol,31.0 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to give a product system containing the structural compound represented by formula 2 v. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a compound of the formula 2v as a colorless liquid, with a separation yield of 52%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.40 (dd, J = 1.8, 0.8 Hz, 1H), 7.08 (dd, J = 3.5, 0.8 Hz, 1H), 6.56 (s, 1H), 6.47 (dd, J = 3.5, 1.8 Hz, 1H), 3.40 (td, J = 7.0, 5.8 Hz, 2H), 1.77 – 1.67 (m, 2H), 1.24 (s, 12H), 0.86 (t, J = 7.7 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 158.5, 148.4, 143.6, 113.9, 112.2, 83.3, 41.3, 24.9, 24.0. 11 B NMR (128 MHz, Chloroform-d) δ 34.26。
example 41
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-2-thiophenecarboxamide (designated 1w,0.2mmol,33.4 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 w. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a structural compound represented by formula 2w as a yellow liquid with a separation yield of 68%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.48 (dd, J = 3.7, 1.2 Hz, 1H), 7.42 (dd, J = 5.0, 1.2 Hz, 1H), 7.03 (dd, J = 5.0, 3.7 Hz, 1H), 6.37 (s, 1H), 3.39 (td, J = 7.0, 5.6 Hz, 2H), 1.71 (p, J = 7.4 Hz, 2H), 1.22 (s, 12H), 0.85 (t, J = 7.6 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 161.9, 139.3, 129.5, 127.7, 127.4, 83.3, 42.0, 24.7, 23.7. 11 B NMR (128 MHz, Chloroform-d) δ 34.05。
example 42
Infantile naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-benzo [1, 3-dioxolane ] 5-carboxamide (designated as 1X,0.2mmol,41.0 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added thereto and stirred at room temperature for 1h to give a product system containing the structural compound represented by formula 2X. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a compound of formula 2x as a white solid with a separation yield of 62%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.33 – 7.23 (m, 2H), 6.81 (d, J = 8.0 Hz, 1H), 6.42 (s, 1H), 6.01 (s, 2H), 3.41 (td, J = 6.9, 5.4 Hz, 2H), 1.73 (p, J = 7.2 Hz, 2H), 1.24 (s, 12H), 0.88 (t, J = 7.5 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.9, 150.2, 147.9, 129.3, 121.5, 108.0, 107.7, 101.7, 83.4, 42.3, 24.9, 23.6. 11 B NMR (128 MHz, Chloroform-d) δ 34.09。
example 43
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-2-ferrocenecarboxamide (designated 1y,0.2mmol,53.8 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 y. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a structural compound represented by formula 2y as a yellow liquid with a separation yield of 45%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 5.88 (s, 1H), 4.64 (s, 2H), 4.31 (s, 2H), 4.19 (s, 5H), 3.35 (q, J = 6.7 Hz, 2H), 1.69 (p, J = 7.5 Hz, 2H), 1.25 (s, 12H), 0.86 (t, J = 7.8 Hz, 3H). 13 C NMR (101 MHz, Chloroform-d) δ 170.2, 83.3, 70.3, 69.8, 68.1, 41.7, 24.9, 24.2. 11 B NMR (128 MHz, Chloroform-d) δ 34.46。
example 44
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N- (1-methylcyclopropyl) -benzamide (designated 1z,0.2mmol,35.0 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 z. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to give the compound of formula 2z as a white solid in a separation yield of 71%.
The chemical reaction formula of the preparation process is as follows:
/>
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.78 – 7.70 (m, 2H), 7.48 – 7.35 (m, 3H), 6.22 (d, J = 8.1 Hz, 1H), 4.11 (ddd, J = 14.0, 8.0, 6.6 Hz, 1H), 1.72 – 1.60 (m, 2H), 1.21 (d, J = 6.6 Hz, 3H), 1.19 (s, 12H), 0.89 – 0.82 (m, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.1, 135.3, 131.2, 128.5, 127.0, 83.3, 47.6, 30.6, 24.9, 24.7, 20.8. 11 B NMR (128 MHz, Chloroform-d) δ 34.10。
example 45
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N- (1-phenylcyclopropyl) -benzamide (designated 1aa,0.2mmol,47.4 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 aa. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as eluent, the solvent was dried under reduced pressure to give the structural compound of formula 2aa as a white solid with a separation yield of 71%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.82 – 7.74 (m, 2H), 7.51 – 7.23 (m, 8H), 6.77 (d, J = 7.8 Hz, 1H), 5.11 (q, J = 7.4 Hz, 1H), 2.04 – 1.97 (m, 2H), 1.20 (s, 12H), 0.91 – 0.81 (m, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.0, 142.6, 135.0, 131.5, 128.7, 128.6, 127.3, 127.1, 126.6, 83.5, 55.9, 30.6, 25.0, 24.7. 11 B NMR (128 MHz, Chloroform-d) δ 33.95。
example 46
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N- (1-phenylcyclopropyl) -benzamide (designated 1aa,0.2mmol,47.4 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 aa. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as eluent, the solvent was dried under reduced pressure to give the structural compound of formula 2aa as a white solid with a separation yield of 71%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.82 – 7.74 (m, 2H), 7.51 – 7.23 (m, 8H), 6.77 (d, J = 7.8 Hz, 1H), 5.11 (q, J = 7.4 Hz, 1H), 2.04 – 1.97 (m, 2H), 1.20 (s, 12H), 0.91 – 0.81 (m, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 167.0, 142.6, 135.0, 131.5, 128.7, 128.6, 127.3, 127.1, 126.6, 83.5, 55.9, 30.6, 25.0, 24.7. 11 B NMR (128 MHz, Chloroform-d) δ 33.95。
example 47
Infantile naphtholborane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N- (1- (2-cyclopentenyl) cyclopropyl) -benzamide (designated as 1ab,0.2mmol,51.0 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 ab. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried by spin-drying under reduced pressure to obtain a structural compound represented by formula 2ab as a white solid with an isolation yield of 34%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.80 – 7.71 (m, 2H), 7.51 – 7.34 (m, 3H), 6.16 (d, J = 7.9 Hz, 1H), 5.44 (q, J = 10.0 Hz, 1H), 5.19 (ddd, J = 10.5, 9.2, 1.0 Hz, 1H), 4.85 (p, J = 7.6 Hz, 1H), 2.90 (h, J = 8.6 Hz, 1H), 1.92 – 1.78 (m, 1H), 1.68 – 1.52 (m, 8H), 1.21 (s, 12H), 0.94 – 0.84 (m, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 166.4, 138.6, 136.3, 135.1, 131.1, 128.4, 128.0, 126.9, 83.2, 52.9, 49.3, 42.9, 38.7, 33.9, 33.8, 33.0, 29.9, 29.3, 25.4, 25.4, 25.1, 24.8, 24.7, 24.6. 11 B NMR (128 MHz, Chloroform-d) δ 33.72。
example 48
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N- (2-phenylcyclopropyl) -benzamide (designated 1ac,0.2mmol,47.4 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 ac. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to give a structural compound represented by formula 2ac as a white solid with a separation yield of 37%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.65 – 7.58 (m, 2H), 7.49 – 7.41 (m, 1H), 7.39 – 7.27 (m, 6H), 7.24 – 7.19 (m, 1H), 6.13 (s, 1H), 3.82 (dt, J = 13.0, 6.4 Hz, 1H), 3.48 (ddd, J = 13.3, 8.4, 5.0 Hz, 1H), 3.22 – 3.14 (m, 1H), 1.28 – 1.25 (m, 2H), 1.11 (d, J = 7.5 Hz, 12H). 13 C NMR (101 MHz, Chloroform-d) δ 167.3, 144.2, 134.8, 131.2, 128.6, 128.4, 127.5, 126.8, 126.7, 83.3, 47.2, 41.1, 24.7, 24.5. 11 B NMR (128 MHz, Chloroform-d) δ 33.69。
example 49
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N- (2- (3, 4-difluorophenyl) cyclopropyl) -benzamide (designated 1ad,0.2mmol,54.6 mg) were mixed under nitrogen (1 atm) atmosphere and stirred at 120℃for 12h, after which triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to give a product system containing the structural compound of formula 2 ad. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a structural compound represented by formula 2ad as a white solid with an isolation yield of 42%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.64 (dd, J = 7.0, 1.6 Hz, 2H), 7.50 – 7.44 (m, 1H), 7.43 – 7.35 (m, 2H), 7.17 – 6.95 (m, 4H), 6.18 (s, 1H), 3.73 (dt, J = 13.1, 6.4 Hz, 1H), 3.49 (ddd, J = 13.6, 8.1, 5.4 Hz, 1H), 3.18 (p, J = 7.4 Hz, 1H), 1.26 (td, J = 7.1, 6.4, 3.4 Hz, 2H), 1.12 (d, J = 9.0 Hz, 12H). 13 C NMR (101 MHz, Chloroform-d) δ 167.5, 141.5, 134.7, 131.5, 128.6, 126.9, 123.5, 117.4, 117.2, 116.5, 116.4, 83.6, 47.2, 40.7, 24.8, 24.7. 11 B NMR (128 MHz, Chloroform-d) δ 33.88. 19 F NMR (376 MHz, Chloroform-d) δ -137.63, -140.83。
example 50
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-1-methylcyclohexyl-1-carboxamide (designated 1ae,0.2mmol,36.2 mg) were mixed under nitrogen (1 atm) atmosphere and stirred at 120℃for 12h, after which triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to give a product system containing the structural compound represented by formula 2 ae. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a structural compound represented by formula 2ae as a colorless liquid with a separation yield of 66%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 5.78 (s, 1H), 3.21 (td, J= 7.2, 5.5 Hz, 2H), 1.85 (ddd, J = 12.5, 6.9, 2.5 Hz, 2H), 1.63 – 1.54 (m, 2H), 1.53 – 1.26 (m, 8H), 1.22 (s, 12H), 1.10 (s, 3H), 0.77 (t, J = 7.8 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 177.6, 83.2, 42.6, 41.5, 35.7, 25.9, 24.8, 23.9, 22.9. 11 B NMR (128 MHz, Chloroform-d) δ 34.00。
example 51
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-1-adamantylformamide (designated 1af,0.2mmol,43.8 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 150℃for 12h, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to give a product system containing the structural compound represented by formula 2 af. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a compound of the formula 2af as a colorless liquid with a separation yield of 72%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 5.73 (s, 1H), 3.21 (td, J= 7.1, 5.5 Hz, 2H), 2.05 – 2.01 (m, 3H), 1.84 (d, J = 3.0 Hz, 6H), 1.76 – 1.66 (m, 6H), 1.64 – 1.56 (m, 2H), 1.25 (s, 12H), 0.79 (t, J = 7.9 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 177.9, 83.2, 41.4, 40.6, 39.4, 36.6, 28.2, 24.9, 23.9, 8.2. 11 B NMR (128 MHz, Chloroform-d) δ 33.88。
example 52
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl-1-cyclohexenyl-1-carboxamide (designated 1ag,0.2mmol,33.0 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12h, then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1h to give a product system containing the structural compound represented by formula 2 ag. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a structural compound represented by formula 2ag as a colorless liquid with a separation yield of 50%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 6.59 (tt, J = 3.8, 1.8 Hz, 1H), 5.90 (s, 1H), 3.29 (td, J = 7.0, 5.6 Hz, 2H), 2.22 (tq, J = 6.2, 2.1 Hz, 2H), 2.17 – 2.12 (m, 2H), 1.69 – 1.55 (m, 6H), 1.24 (s, 12H), 0.82 (t, J= 7.8 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 168.8, 133.6, 132.9, 83.3, 41.7, 25.4, 24.9, 24.4, 23.9, 22.3, 21.7. 11 B NMR (128 MHz, Chloroform-d) δ 33.83。
example 53
Infantile naphthol borane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropyl pivaloyl amide (designated as 1ah,0.2mmol,28.2 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 ah. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a structural compound represented by formula 2ah as a colorless liquid with a separation yield of 59%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 5.78 (s, 1H), 3.26 – 3.14 (m, 2H), 1.59 (p, J = 7.6 Hz, 2H), 1.23 (s, 12H), 1.16 (s, 9H), 0.77 (t, J = 7.8 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 178.4, 83.3, 41.6, 38.7, 27.7, 24.9, 23.9. 11 B NMR (128 MHz, Chloroform-d) δ 34.04。
example 54
Infantile naphthol borane (designated as HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N- (1- (2-cyclopentenyl) cyclopropyl) -pivalamide (designated as 1ai,0.2mmol,47.0 mg) were mixed under nitrogen (1 atm) atmosphere and stirred at 120℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 ai. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as eluent, the solvent was dried under reduced pressure to obtain a compound of formula 2ai as a colorless liquid with a separation yield of 56%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 5.54 – 5.34 (m, 2H), 5.31 – 4.99 (m, 1H), 4.65 – 4.26 (m, 1H), 2.89 – 2.30 (m, 1H), 1.78 – 1.52 (m, 9H), 1.22 (s, 13H), 1.16 (d, J = 9.7 Hz, 9H), 0.74 (ddd, J = 9.0, 6.7, 1.8 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 177.5, 177.2, 138.7, 136.0, 128.3, 128.2, 83.2, 52.2, 48.7, 43.0, 38.7, 38.6, 34.0, 33.9, 33.1, 33.1, 30.0, 29.5, 27.7, 27.7, 25.5, 25.4, 25.1, 24.9, 24.9. 11 B NMR (128 MHz, Chloroform-d) δ 34.66。
example 55
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropylthio pivalamide (designated 1aj,0.2mmol,31.4 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 150℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 aj. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a structural compound represented by formula 2aj as a yellow liquid with a separation yield of 43%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 7.53 (s, 1H), 3.63 (td, J= 7.2, 5.0 Hz, 2H), 1.83 – 1.71 (m, 2H), 1.34 (s, 9H), 1.25 (s, 12H), 0.85 (t, J = 7.8 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 213.1, 83.5, 48.7, 44.5, 30.2, 24.9, 22.3. 11 B NMR (128 MHz, Chloroform-d) δ 34.08。
example 56
Infantile naphthol borane (designated HBcat,0.4mmol, 42.7. Mu.L), toluene (2 mL) and N-cyclopropylthiobenzamide (designated 1aj,0.2mmol,35.4 mg) were mixed under nitrogen (1 atm) atmosphere, stirred at 150℃for 12 hours, and then triethylamine (0.6 mmol, 84. Mu.L) and pinacol (0.6 mmol,70.8 mg) were added and stirred at room temperature for 1 hour to give a product system containing the structural compound represented by formula 2 aj. The product was then purified by column chromatography on silica gel using methylene chloride: after eluting with ethyl acetate (volume ratio of 15:1) as an eluent, the solvent was dried under reduced pressure to obtain a structural compound represented by formula 2aj as a yellow liquid with a separation yield of 32%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1 H NMR (400 MHz, Chloroform-d) δ 8.32 (s, 1H), 7.78 – 7.71 (m, 2H), 7.56 – 7.29 (m, 3H), 3.79 (td, J = 6.6, 4.9 Hz, 2H), 1.90 (p, J = 7.0 Hz, 2H), 1.17 (s, 12H), 0.97 (t, J = 7.2 Hz, 2H). 13 C NMR (101 MHz, Chloroform-d) δ 199.2, 142.4, 130.9, 128.5, 126.9, 83.7, 49.4, 24.8, 22.1. 11 B NMR (128 MHz, Chloroform-d) δ 34.19。
the foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (5)

1. A reaction method for ring-opening boronation of cyclopropane compounds under metal-free catalysis is characterized in that: the method comprises the steps of mixing and heating cyclopropane compounds, naphthol borane and an organic solvent in a protective atmosphere to carry out a boration reaction, and stirring the mixture for 1 hour at room temperature by triethylamine and pinacol to obtain boron-containing compounds;
The structural formula of the cyclopropane compound is shown as follows:
；
the structural formula of the boron-containing compound is shown as follows:
wherein: r is R 1 Is one of beta-naphthalene, aromatic heterocycle, phenyl, substituted phenyl or alkyl; the R is 2 Is one of phenyl, alkyl or hydrogen; the R is 3 Is one of phenyl, substituted phenyl or hydrogen; the substituent in the substituted phenyl is one of methyl, fluorine, chlorine, bromine, tertiary butyl, phenyl, trifluoromethyl, cyano, ester, N-dimethyl, acetyl, nitro or methoxy; x is oxygen or sulfur.
2. The method for ring-opening boronation of cyclopropane compounds under metal-free catalysis of claim 1, wherein the method comprises the following steps: the molar ratio of the cyclopropane compound to the naphthol borane to the pinacol is 1: (1.2 to 3.0): (1.2-3.0); the molar ratio of the triethylamine to the pinacol is 1:1.
3. the method for ring-opening boronation of cyclopropane compounds under metal-free catalysis of claim 1, wherein the method comprises the following steps: the organic solvent is one of toluene, tetrahydrofuran, paraxylene, 1, 4-dioxane, 1, 2-dichloroethane, diethylene glycol dimethyl ether or methyl tertiary butyl ether.
4. The method for ring-opening boronation of cyclopropane compounds under metal-free catalysis of claim 1, wherein the method comprises the following steps: the condition of the boration reaction is that the temperature is 100-150 ℃ and the time is 6-48 h.
5. The method for ring-opening boronation of cyclopropane compounds under metal-free catalysis of claim 1, wherein the method comprises the following steps: the protective atmosphere is nitrogen atmosphere or argon atmosphere.
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