Citation: Wang Yang, Lan Yu. Mechanism and origin of diastereoselectivity of N-heterocyclic carbene-catalyzed cross-benzoin reaction: A DFT study[J]. Chinese Chemical Letters, ;2020, 31(3): 736-738. doi: 10.1016/j.cclet.2019.08.010 shu

Mechanism and origin of diastereoselectivity of N-heterocyclic carbene-catalyzed cross-benzoin reaction: A DFT study

Wang Yang ^a ,
Lan Yu ^b,c,*,

a.
Department of Material and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450002, China
b.
College of Chemistry, Zhengzhou University, Zhengzhou 450001, China
c.
School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing 4000030, China

lanyu@cqu.edu.cn

Received Date: 1 August 2019
Revised Date: 7 August 2019
Accepted Date: 8 August 2019
Available Online: 8 August 2019

Figures(5)

Herein, the origin of the diastereoselectivity of N-heterocyclic carbene (NHC)-catalyzed cross-benzoin reactions between an α-amino aldehyde and furfural was studied by density functional theory. The computational results showed that the reaction proceeded through four steps:nucleophilic addition of NHC onto furfural, formation of a Breslow intermediate, cross-coupling reaction between Breslow intermediate and α-amino aldehyde, and dissociation of the catalyst. The cross-coupling was identified as the diastereoselectivity-determining step, with the R-configured product generated preferentially. Noncovalent interaction (NCI) analysis showed that the C-H … O and C-H … F interactions were responsible for determining the diastereoselectivity.
- Reaction mechanism,
- DFT calculations,
- N-Heterocyclic carbine,
- Cross-benzoin,
- Diastereoselectivity
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