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Formal Asymmetric Catalytic Thiolation with a Bifunctional Catalyst at a Water–Oil Interface: Synthesis of Benzyl Thiols
Author(s) -
Guo Wengang,
Wu Bo,
Zhou Xin,
Chen Ping,
Wang Xu,
Zhou YongGui,
Liu Yan,
Li Can
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201409894
Subject(s) - squaramide , chemistry , moiety , bifunctional , enantioselective synthesis , stereoselectivity , catalysis , bifunctional catalyst , organic chemistry , reactivity (psychology) , amine gas treating , organocatalysis , solvent , combinatorial chemistry , medicine , alternative medicine , pathology
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.