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Method for synthesizing trisubstituted alkenyl borate through copper-catalyzed three-component reaction

A technology of alkenyl borate and tri-substitution, which is applied in the field of synthesizing alkenyl borate, can solve the problems that the synthesis of tri-substituted alkenyl borate has not yet been realized, and achieve wide application range of substrates, simple reaction operation, The effect of high yield

Active Publication Date: 2021-07-27
CHANGZHOU UNIV
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

[0003] Borylation of N-sulfonylhydrazones with boron reagents is also an effective method for the synthesis of organoboron compounds (Li, H.; Wang, L.; Zhang, Y.; Wang, J. Angew. Chem., Int. Ed. 2012 ,51,2943.Li,H.; Shangguan,X.; Zhang,Z.; Huang,S.; Zhang,Y.; Wang,J.Org.Lett.2014,16,448.), although the synthesis of alkenyl boronic acid There are many methods for esters, but the synthesis of trisubstituted alkenyl boronic acid esters by three-component one-pot reaction with difunctionalization at the same alkyne terminal carbon has not yet been realized.

Method used

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  • Method for synthesizing trisubstituted alkenyl borate through copper-catalyzed three-component reaction
  • Method for synthesizing trisubstituted alkenyl borate through copper-catalyzed three-component reaction
  • Method for synthesizing trisubstituted alkenyl borate through copper-catalyzed three-component reaction

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Embodiment 1: Synthesis of 4a:

[0032]

[0033] Under argon protection, add 1a (20.4 mg), B 2 (pin) 2 (152.3mg), CuI (3.1mg), 2,2'-bipyridine (3.1mg), Molecular sieves (100 mg) and DMF (2 mL) were added after which 2a (52.8 mg) dissolved in DMF (2 mL) was added; the reaction mixture was stirred on a 30°C heating block for 18 hours. The reaction solution was diluted with 10 mL of water and extracted with ethyl acetate; the organic phase was dried and the solvent was removed under reduced pressure; the crude product was purified by column chromatography and washed with ethyl acetate:petroleum ether (1:20) to obtain a colorless oily product 4a (66.6 mg, 88%, Z:E>19:1). 1 H NMR (300MHz, CDCl3) δ7.49(s,1H),7.33-7.26(m,6H),7.26-7.17(m,4H),4.89(s,1H),3.67(s,3H),1.30( s,6H), 1.29(s,6H). 13C NMR (75MHz, CDCl3) δ173.8, 144.4, 139.5, 137.1, 129.4, 128.8, 128.34, 128.3, 127.7, 126.9, 83.9, 52.2, 51.2, 24.9, 24.8. HRMS (ESI) m / z: [M+Na] +Calcd for C 23 h 27 BNaO 4 401...

Embodiment 2

[0034] Embodiment 2: Synthesis of 4a:

[0035]

[0036] Under argon protection, add 1a (20.4 mg), B 2 (pin) 2 (152.3mg), CuI (3.1mg), 2,2'-bipyridine (3.1mg), Molecular sieves (100 mg) and DMSO (2 mL) were added followed by 2a (52.8 mg) dissolved in DMSO (2 mL); the reaction mixture was stirred on a 30°C heating block for 18 hours. The reaction solution was diluted with 10 mL of water and extracted with ethyl acetate; the organic phase was dried and the solvent was removed under reduced pressure; the crude product was purified by column chromatography and washed with ethyl acetate:petroleum ether (1:20) to obtain a colorless oily product 4a (30.2 mg, 40%, Z:E>19:1).

Embodiment 3

[0037] Embodiment 3: Synthesis of 4a:

[0038]

[0039] Under argon protection, add 1a (20.4 mg), B 2 (pin) 2 (101.5mg), CuI (3.1mg), 2,2'-bipyridine (3.1mg), Molecular sieves (100 mg) and DMF (2 mL) were added after which 2a (52.8 mg) dissolved in DMF (2 mL) was added; the reaction mixture was stirred on a 30°C heating block for 18 hours. The reaction solution was diluted with 10 mL of water and extracted with ethyl acetate; the organic phase was dried and the solvent was removed under reduced pressure; the crude product was purified by column chromatography and washed with ethyl acetate:petroleum ether (1:20) to obtain a colorless oily product 4a (38.6 mg, 51%, Z:E>19:1).

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Abstract

The invention belongs to the field of organic synthesis, particularly relates to a method for synthesizing trisubstituted alkenyl borate through a copper-catalyzed three-component reaction, and provides a method for synthesizing trisubstituted alkenyl borate through a stereoselective copper-catalyzed terminal alkyne, duplex pinacol borate and a diazo compound or N-sulfonyl hydrazone one-pot method. According to the method, bifunctionalization is selectively carried out at the tail end of terminal alkyne, when a diazo compound is used as a carbene precursor, (Z)-trisubstituted alkenyl borate is obtained with high stereoselectivity, and when N-sulfonyl hydrazone is used, (E)-trisubstituted alkenyl borate is obtained. The method disclosed by the invention has the advantages that the three-component series one-pot reaction is realized, the operation is simple, the raw materials are simple and easy to obtain, the reaction yield is high, the substrate application range is wide, and the (E) / (Z) stereoselectivity is good and controllable.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a method for synthesizing alkenyl borate in one pot using copper-catalyzed terminal alkyne, double pinacol borate and diazo compound or sulfonyl hydrazone. Background technique [0002] Organoborates are a class of organic reagents with important synthetic application value, and are widely used in cross-coupling reactions. As the most common synthons of complex olefin derivatives, alkenyl borates can be used to synthesize alkenyl-containing target molecules. At present, the main method for the synthesis of alkenyl borates is prepared by metal-catalyzed borylation of alkenes, allenes or alkynes with boron reagents (Moure, A.L., et al. J. Am. Chem. Soc. 2012, 134, 7219 .Reid, W.B.;, et al.Org.Lett.2018,20,6832.Magre,M.,et al.Angew.Chem.Int.Ed.2019,58,7025.Brzozowska,A.,et al.Org. Lett.2020,22,3765.Guo,W.-H.,et al.ACSCatal.2019,9,38.Hu,Y.,et al.Angew.Chem.Int.Ed.2019,5...

Claims

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Application Information

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IPC IPC(8): C07F5/02
CPCC07F5/025C07B2200/09
Inventor 孙江涛许光洋李自永邵莺唐生表
Owner CHANGZHOU UNIV
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