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Gold(I)/Chiral N , N′ ‐Dioxide–Nickel(II) Relay Catalysis for Asymmetric Tandem Intermolecular Hydroalkoxylation/Claisen Rearrangement
Author(s) -
Li Jun,
Lin Lili,
Hu Bowen,
Zhou Pengfei,
Huang Tianyu,
Liu Xiaohua,
Feng Xiaoming
Publication year - 2017
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.201611214
Subject(s) - chemistry , allylic rearrangement , catalysis , claisen rearrangement , nickel , tandem , cascade reaction , intermolecular force , asymmetric induction , lewis acids and bases , combinatorial chemistry , medicinal chemistry , enantioselective synthesis , organic chemistry , molecule , materials science , composite material
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.