Herein, a facile synthesis of valuable pyrido[1,2-a]pyrimidine-4-thiones is reported via novel thiocarbonylation of C(sp^(3))-H bonds with carbon disulfide(CS_(2)). This reaction features easy availability of substrat...Herein, a facile synthesis of valuable pyrido[1,2-a]pyrimidine-4-thiones is reported via novel thiocarbonylation of C(sp^(3))-H bonds with carbon disulfide(CS_(2)). This reaction features easy availability of substrates,good functional group tolerance, high yields, facile scalability and atom economy. Mechanistic investigations indicate that sulfate anion and sulfuric anhydride anion might be involved in this reaction.展开更多
A general and straightforward strategy for the synthesis of thioester-substituted oxindoles via a palladium-catalyzed thiocarbonyla-tive cyclization process has been developed.With sulfonyl chlorides as promising sulf...A general and straightforward strategy for the synthesis of thioester-substituted oxindoles via a palladium-catalyzed thiocarbonyla-tive cyclization process has been developed.With sulfonyl chlorides as promising sulfur source,a wide range of thioester-substituted oxindoles were obtained in moderate to high yields.Both aryl and alkyl sulfonyl chlorides were well tolerated,and Mo(CO)6 played a dual role as both a CO source and a reductant in this approach.展开更多
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
基金the National Natural Science Foundation of China (No. 21822108)Sichuan Science and Technology Program (Nos.20CXTD0112, 2020YJ0491)+1 种基金National Key Research and Development Program of China (No. 2018YFC1602101)the Fundamental Research Funds for the Central Universities。
文摘Herein, a facile synthesis of valuable pyrido[1,2-a]pyrimidine-4-thiones is reported via novel thiocarbonylation of C(sp^(3))-H bonds with carbon disulfide(CS_(2)). This reaction features easy availability of substrates,good functional group tolerance, high yields, facile scalability and atom economy. Mechanistic investigations indicate that sulfate anion and sulfuric anhydride anion might be involved in this reaction.
基金We thank the financial supports from the Natural Science Foundationof Zhejiang Province(LY21B020010).
文摘A general and straightforward strategy for the synthesis of thioester-substituted oxindoles via a palladium-catalyzed thiocarbonyla-tive cyclization process has been developed.With sulfonyl chlorides as promising sulfur source,a wide range of thioester-substituted oxindoles were obtained in moderate to high yields.Both aryl and alkyl sulfonyl chlorides were well tolerated,and Mo(CO)6 played a dual role as both a CO source and a reductant in this approach.
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.
