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
DOI:10.1007/s11426-023-1795-9
日期:2024.3
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
描述了在没有镍或铜催化的情况下,使用掩蔽硫转移试剂对烷基亲电子试剂进行锌促进的还原硫醇化。该方案通过Zn 与亲电硫试剂的 SET 过程进行,然后将 Zn 插入二硫化物和亲核硫醇化,从而可以直接获得具有广泛底物范围的各种烷基硫醚。合成、分离并通过 NMR、IR 和 X 射线分析充分表征了具有四面体几何形状的中性 TMEDA 连接的四配位硫醇锌。更重要的是,这种活性中间体的化学反应性已经得到研究,能够构建 C-Se、C-Te、Sb-S 和 Bi-S 键,以制备有价值的含硫分子等。