N-Heterocyclic Carbene Catalyzed Asymmetric Intermolecular Stetter Reaction: Origin of Enantioselectivity and Role of Counterions

被引:46
|
作者
Kuniyil, Rositha [1 ]
Sunoj, Raghavan B. [1 ]
机构
[1] Indian Inst Technol, Dept Chem, Bombay 400076, Maharashtra, India
关键词
MECHANISTIC INSIGHTS; STEREOSELECTIVITY; ALDEHYDES; ENALS;
D O I
10.1021/ol402375d
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The mechanism and the role of KOtBu in an enantioselective NHC-catalyzed Stetter reaction between p-chlorobenzaldehyde and N-acylamido acrylate is established using DFT(M06-2X) methods. The Gibbs free energies are found to be significantly lower for transition states with explicit bound KOtBu as compared to the conventional pathways without the counterions. An intermolecular proton transfer from HOtBu to the prochiral carbon is identified as the stereocontrolling step. The computed enantioselectivities are in excellent agreement with the experimental results.
引用
收藏
页码:5040 / 5043
页数:4
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