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Palladium‐Catalyzed Enantioselective Thiocarbonylation of Styrenes
Author(s) -
Wang Xihong,
Wang Bing,
Yin Xuemei,
Yu Wangzhi,
Liao Yang,
Ye Jialin,
Wang Min,
Hu Lianrui,
Liao Jian
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201905905
Subject(s) - enantioselective synthesis , thioester , chemistry , catalysis , palladium , combinatorial chemistry , acylation , phosphine , catalytic cycle , sulfoxide , substrate (aquarium) , organic chemistry , oceanography , enzyme , geology
A highly enantioselective thiocarbonylation of styrenes with CO and thiols has been achieved by Pd catalysis, providing highly enantioenriched thioesters in good to excellent yields. Key to the successful execution of this reaction is the use of a chiral sulfoxide‐(P‐dialkyl)‐phosphine (SOP) ligands. This thiocarbonylation proceeds smoothly under mild reaction conditions (1 atm CO and 0 °C) and displays broad substrate scope. Also demonstrated is that this transformation can be conducted using surrogates of CO, greatly increasing the safety aspects of running the reaction. The generality and utility of the method is manifested by its application to the synthetic transformations of thioester products and the direct acylation of cysteine‐containing dipeptides. A primary mechanism was investigated and a plausible catalytic cycle was proposed.