Bimetallic Gold(I)/Chiral N,N′-Dioxide Nickel(II) Asymmetric Relay Catalysis: Chemo- and Enantioselective Synthesis of Spiroketals and Spiroaminals

A highly efficient asymmetric cascade reaction between keto esters and alkynyl alcohols and amides is reported. The success of the reaction was attributed to the combination of chiral Lewis acid N,N′‐dioxide nickel(II) catalysis with achiral π‐acid gold(I) catalysis working as an asymmetric relay ca...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2016-05, Vol.55 (20), p.6075-6078
Main Authors: Li, Jun, Lin, Lili, Hu, Bowen, Lian, Xiangjin, Wang, Gang, Liu, Xiaohua, Feng, Xiaoming
Format: Article
Language:English
Subjects:
Alcohols
Amides
asymmetric catalysis
Asymmetry
Bimetals
Cascade chemical reactions
cascade reactions
Catalysis
Chemical synthesis
Dioxides
Enantiomers
Esters
Gold
Lewis acid
Nickel
relay catalysis
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Summary:A highly efficient asymmetric cascade reaction between keto esters and alkynyl alcohols and amides is reported. The success of the reaction was attributed to the combination of chiral Lewis acid N,N′‐dioxide nickel(II) catalysis with achiral π‐acid gold(I) catalysis working as an asymmetric relay catalytic system. The corresponding spiroketals and spiroaminals were synthesized in up to 99 % yield, 19:1 d.r., and more than 99 % ee under mild reaction conditions. Control experiments suggest that the N,N′‐dioxide ligand was essential for the formation of the spiro products. Running a relay: Highly efficient asymmetric cascade reactions of keto esters with alkynyl alcohols and amides were achieved using a gold(I)/chiral N,N′‐dioxide nickel(II) complex as a bimetallic relay catalytic system. A variety of spiroketals and spiroaminals could be obtained using this method.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201601701