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In Situ Formed Bifunctional Primary Amine‐Imine Catalyst: Application to the Construction of Chiral Tertiary Alcohols through Asymmetric Aldol‐Type Reaction
Author(s) -
Mao Zhijie,
Zhu Xi,
Lin Aijun,
Li Weipeng,
Shi Yan,
Mao Haibin,
Zhu Chengjian,
Cheng Yixiang
Publication year - 2013
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201300108
Subject(s) - chemistry , imine , enamine , aldol reaction , bifunctional , amine gas treating , catalysis , organocatalysis , organic chemistry , ketone , tertiary amine , medicinal chemistry , enantioselective synthesis
An in situ formation method to obtain chiral bifunctional primary amine‐imine catalysts from the C 2 ‐symmetric chiral diimines has been developed. The efficiency of this method in the construction of chiral tertiary alcohols which are valuable pharmaceutical intermediates is proved by its application to the asymmetric aldol‐type reaction of cyclic ketones with other activated ketone compounds as the enamine acceptors, i.e., β,γ‐unsaturated α‐keto esters and isatins. In general, good to excellent diastereoselectivities and enantioselectivities (up to 96/4 dr , 96% ee for β,γ‐unsaturated α‐keto esters and up to 91/9 dr , 94% ee for isatins) were obtained. The active primary amine‐imine catalylst and enamine intermediate in the reaction process could be demonstrated by ESI‐MS analysis.