Gold(I)/Chiral N,N′-Dioxide-Nickel(II) Relay Catalysis for Asymmetric Tandem Intermolecular Hydroalkoxylation/Claisen Rearrangement

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• 作者：Jun Li ; Dr. Lili Lin ; Bowen Hu ; Pengfei Zhou ; Tianyu Huang ; Prof. Dr. Xiaohua Liu and Prof. Dr. Xiaoming Feng
• 刊名：Angewandte Chemie International Edition
• 出版年：2017
• 出版时间：January 16, 2017
• 年：2017
• 卷：56
• 期：3
• 页码：885-888
• 全文大小：731K
• ISSN：1521-3773

文摘

A highly efficient asymmetric cascade reaction between alkynyl esters and allylic alcohols has been realized. Key to success was the combination of a hydroalkoxylation reaction catalyzed by a π-acidic gold(I) complex with a Claisen rearrangement catalyzed by a chiral Lewis acidic N,N′-dioxide–nickel(II) complex. A range of acyclic α-allyl β-keto esters were synthesized in high yields (up to 99 %) with good diastereoselectivities (up to 97:3) and excellent enantioselectivities (up to 99 % ee) under mild reaction conditions. These products can be easily transformed into optically active β-hydroxy esters, β-hydroxy acids, or 1,3-diols.