Enantioselective carbon–sulfur bond formation: γ additions of aryl thiols to allenoates catalyzed by a chiral phosphepine
Author(s)Fujiwara, Yuji; Sun, Jianwei; Fu, Gregory C.
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An effective phosphine-catalyzed method was developed for the enantioselective addition of aryl thiols to the γ position of allenoates, thereby providing ready access to aryl alkyl sulfides in very good ee. The array of mechanistic data are consistent with the addition of the chiral phosphine to the allenoate being the turnover-limiting step of the catalytic cycle. The optimized reaction conditions, as well as the mechanistic observations, differ markedly from an earlier report on asymmetric additions of alkyl thiols to allenoates, which highlights the potential for divergent behavior between alkyl and aryl thiols when acting as nucleophiles.
DepartmentMassachusetts Institute of Technology. Department of Chemistry
Royal Society of Chemistry, The
Fujiwara, Yuji, Jianwei Sun, and Gregory C. Fu. “Enantioselective carbon–sulfur bond formation: γ additions of aryl thiols to allenoates catalyzed by a chiral phosphepine.” Chemical Science 2, no. 11 (2011): 2196.
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