Asymmetric Catalysis via Cyclic, Aliphatic Oxocarbenium Ions

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• 作者：Sunggi Lee ; Philip S. J. Kaib ; Benjamin List
• 刊名：Journal of the American Chemical Society
• 出版年：2017
• 出版时间：February 15, 2017
• 年：2017
• 卷：139
• 期：6
• 页码：2156-2159
• 全文大小：414K
• ISSN：1520-5126

文摘

A direct enantioselective synthesis of substituted oxygen heterocycles from lactol acetates and enolsilanes has been realized using a highly reactive and confined imidodiphosphorimidate (IDPi) catalyst. Various chiral oxygen heterocycles, including tetrahydrofurans, tetrahydropyrans, oxepanes, chromans, and dihydrobenzofurans, were obtained in excellent enantioselectivities by reacting the corresponding lactol acetates with diverse enol silanes. Mechanistic studies suggest the reaction to proceed via a nonstabilized, aliphatic, cyclic oxocarbenium ion intermediate paired with the confined chiral counteranion.