Copper-Catalyzed Highly Stereoselective Hydrodifluoroallylation of Cyclopropenes and Alkenyl Boronates with 3,3-Difluoroallyl Sulfonium Salts  

作　　者：Xing Gao Xiaoxiao Ren Wei Deng Xingang Zhang 

机构地区：[1]Key Laboratory of Organofluorine Chemistry,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences, Chinese Academy of Sciences,345 Lingling Road,Shanghai,200032 China [2]School of Chemistry and Material Sciences,Hangzhou Institute for Advanced Study,University of Chinese Academy of Sciences,1 Sub-lane Xiangshan,Hangzhou,Zhejiang,310024 China

出　　处：《Chinese Journal of Chemistry》2023年第24期3521-3527,共7页中国化学（英文版）

基　　金：Financial support for this work was provided by the National Key R&D Program of China(2021YFF0701700);the National Natural Science Foundation of China(21931013,22193072);the Science and Technology Committee of Shanghai Municipality(22JC1403500,21XD1404400).

摘　　要：Despite the paramount applications of organofluorine compounds in life and materials sciences,efficient strategies for stereoselectively constructing the C(sp^(3))-CF_(2)R bond at the stereogenic center remain limited.Here,we report a copper-catalyzed hydrodifluoroallylation of cyclopropenes and alkenyl boronates with 3,3-difluoroallyl sulfonium salts(DFASs).The use of DFASs overcomes the previous challenge of suppressing the reduction of fluoroalkylating reagents with M-H species.The reaction provides an array of gem-difluoroallyl cyclopropanes and borylalkanes with high efficiency and stereoselectivity under mild reaction conditions.Using chiral phosphine ligand could provide gem-difluoroallyl borylalkanes with high enantioselectivities,paving a new way for the catalytic asymmetric fluoroalkylation with ubiquitous alkenes.The advantages of this protocol are synthetic convenience,high functional group tolerance,and the synthetic versatility of the resulting gem-difluoroallyl cyclopropanes and borylalkanes.The synthetic utility of this approach has also been demonstrated by the diversified transformations of the gem-difluoroallylated products and the rapid synthesis of bioactive molecule analogs.

关 键 词：Asymmetric catalysis Copper hydride Cross-coupling Synthetic methods Hydrofluoroalkylation Sulfonium salts 

分 类 号：O62[理学—有机化学]