Bioinspired zinc-mediated umpolung thiolation of alkyl electrophiles: reaction development, scope and mechanism  

作　　者：Yuenian Xu Yan Zhang Yong Liu Wen-Wu Sun Jie Huang Hui He Yingjie Wu Wen Liu Shao-Fei Ni Xu-Qiong Xiao Xinxin Shao 

机构地区：[1]College of Material,Chemistry and Chemical Engineering,Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education,Hangzhou Normal University,Hangzhou 311121,China [2]School of Pharmaceutical Sciences,South-Central Minzu University,Wuhan 430074,China [3]Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guang-dong Province,Shantou University,Shantou 515063,China

出　　处：《Science China Chemistry》2024年第3期898-907,共10页中国科学（化学英文版）

基　　金：the National Science Foundation of China(22001051);Zhejiang Provincial Natural Science Foundation of China(LY23B020002)for financial support;funding from the STU Scientific Research Foundation for Talents(NTF20022)。

摘　　要：Zinc-promoted umpolung thiolation of alkyl electrophiles with masked sulfur transfer reagents in the absence of nickel or copper catalysis is described. This protocol proceeds via a SET process of Zn to electrophilic sulfur reagent followed by insertion of Zn into disulfide and nucleophilic thiolation, providing straightforward access to a wide range of alkyl sulfides with broad substrate scope. A neutral TMEDA-ligated four-coordinated zinc thiolate with tetrahedra geometry was synthesized, isolated and fully characterized by NMR, IR and X-ray analysis. More importantly, the chemical reactivity of this active intermediate has been investigated, enabling the construction of C-Se, C-Te, Sb-S and Bi-S bonds to prepare valuable sulfur-containing molecules and beyond.

关 键 词：umpolung thiolation C(sp^(3))-S bond formation masked sulfur reagents reductive coupling 

分 类 号：TQ031.9[化学工程]