As trifluoromethylthiolation has received increasing attention recently, many CF_3S-reagents and trifluoromethylthiolation methods have been developed. Herein we describe trifluoromethylthiolation of alkyl halides by ...As trifluoromethylthiolation has received increasing attention recently, many CF_3S-reagents and trifluoromethylthiolation methods have been developed. Herein we describe trifluoromethylthiolation of alkyl halides by using Ph_3 P^+CF_2CO_2 as a fluoride and difluorocarbene source. Difluorocarbene is a versatile intermediate, but its side reactions are usually ignored and the by-products would therefore be discarded. In this work, a side reaction of difluorocarbene, the generation of a fluoride anion from difluorocarbene, was developed into a synthetic tool. Although the trifluoromethylthiolation reaction involved multi-sequential steps, the cleavage of C-F bond, the formation of CF_2=S bond, F-C(S)F_2 bond,and C-SCF_3 bond, the conversion proceeded fast and was completed within 10 min.展开更多
Summary of main observation and conclusion CF3S,CF3 and HCF2 groups have been identified as valuable functionalities for drug development.Despite significant accomplishments in the trifluoromethylthiolation,trifluorom...Summary of main observation and conclusion CF3S,CF3 and HCF2 groups have been identified as valuable functionalities for drug development.Despite significant accomplishments in the trifluoromethylthiolation,trifluoromethylation and d讦luoromethylation reactions,directly converting common functional groups into CF3S,CF3 or HCF2 groups is still highly desirable.展开更多
基金the National Basic Research Program of China (No. 2015CB931903)the National Natural Science Foundation of China (Nos. 21421002, 21472222, 21502214, 21672242, 81273537)+7 种基金the Chinese Academy of Sciences (Nos. XDA02020105, XDA02020106)the Key Research Program of Frontier Sciences(CAS)(No. QYZDJSSW-SLH049)the Key Project of Hunan Provincial Education Department(No. 17A190)the Zhengxiang Scholar Program of the University of South China, Hunan Provincial Hengyang City Joint Fund(No. 2017JJ4050)Hunan Graduate Science and Technology Innovation Projects (No. 2018-400)Program for Innovative Talent Team of Hengyang(No. 2017-1)the Key Project of Hengyang Science and Technology Department(No. 2017KJ166)Shanghai Research Institute of Chemical Industry Co., LTD.(No. SKL-LCTP-201802)for financial support
文摘As trifluoromethylthiolation has received increasing attention recently, many CF_3S-reagents and trifluoromethylthiolation methods have been developed. Herein we describe trifluoromethylthiolation of alkyl halides by using Ph_3 P^+CF_2CO_2 as a fluoride and difluorocarbene source. Difluorocarbene is a versatile intermediate, but its side reactions are usually ignored and the by-products would therefore be discarded. In this work, a side reaction of difluorocarbene, the generation of a fluoride anion from difluorocarbene, was developed into a synthetic tool. Although the trifluoromethylthiolation reaction involved multi-sequential steps, the cleavage of C-F bond, the formation of CF_2=S bond, F-C(S)F_2 bond,and C-SCF_3 bond, the conversion proceeded fast and was completed within 10 min.
基金The authors thank the National Natural Science Foundation of China(Nos.21421002,21672242,21971252)the Key Research Program of Frontier Sciences(CAS)(QYZDJSSW-SLH049)+1 种基金Youth Innovation Promotion Association CAS(2019256)Shanghai Research Institute of Chemical Industry Co.,Ltd.(SKL-LCTP-201802)for financial support.
文摘Summary of main observation and conclusion CF3S,CF3 and HCF2 groups have been identified as valuable functionalities for drug development.Despite significant accomplishments in the trifluoromethylthiolation,trifluoromethylation and d讦luoromethylation reactions,directly converting common functional groups into CF3S,CF3 or HCF2 groups is still highly desirable.
