Formal Asymmetric Catalytic Thiolation with a Bifunctional Catalyst at a Water–Oil Interface: Synthesis of Benzyl Thiols

作者：Wengang Guo, Bo Wu, Xin Zhou, Ping Chen, Xu Wang, Yong‐Gui Zhou, Yan Liu, Can Li · 发表于：Angewandte Chemie International Edition · 年份：2015 · DOI：10.1002/anie.201409894 · 被引用次数：126 · 研究领域：Synthesis of Indole Derivatives、Sulfur-Based Synthesis Techniques、Chemical Synthesis and Reactions

The enantioselective conjugated addition of tritylthiol to in situ generated ortho-quinone methides (o-QMs) is catalyzed by an acid-base bifunctional squaramide organocatalyst. The transformation proceeds with high yield (up to 99 %) and stereoselectivity (up to 97:3 e.r.) using water as solvent under mild conditions. The catalyst system provides a new strategy for the synthesis of optically active benzyl mercaptans. Control experiments suggested that o-QMs are generated by the tertiary amine moiety of the squaramide organocatalyst and that the water-oil biphase is crucial for achieving high reactivity and stereoselectivity.