Citation: Chen Haohua, Zhu Lei, Zhong Kangbao, Yue Xiaoyu, Qu Ling-Bo, Bai Ruopeng, Lan Yu. Theoretical insight into phosphoric acid-catalyzed asymmetric conjugate addition of indolizines to α, β-unsaturated ketones[J]. Chinese Chemical Letters, ;2018, 29(8): 1237-1241. doi: 10.1016/j.cclet.2018.03.018 shu

Theoretical insight into phosphoric acid-catalyzed asymmetric conjugate addition of indolizines to α, β-unsaturated ketones

Chen Haohua ^a,1 ,
Zhu Lei ^a,1 ,
Zhong Kangbao ^a ,
Yue Xiaoyu ^a ,
Qu Ling-Bo ^b ,
Bai Ruopeng ^a,, ,
Lan Yu ^a,b,,

a.
School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030, China
b.
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, China

Corresponding author: Bai Ruopeng, ruopeng@cqu.edu.cn Lan Yu, lanyu@cqu.edu.cn

Received Date: 15 January 2018
Revised Date: 5 March 2018
Accepted Date: 16 March 2018
Available Online: 17 August 2018

Figures(6)

Phosphoric acid catalysis is a powerful tool for the construction of new C-C bonds because of its unique LUMO-lowering activity. Theoretical calculations were employed to investigate phosphoric acidcatalyzed asymmetric conjugate addition of indolizines to α, β-unsaturated ketones. The calculation results showed that this transformation proceeds via a reaction pathway involving nucleophilic addition, deprotonation-aromatization, and tautomerization. The computational results showed that deprotonation-aromatization is the rate-determining step and the enantioselectivity-determining step. The S-configured product was preferentially generated via a pathway starting from the s-cis conjugated ketone, whereas the s-trans isomer led to a side product with the R configuration. Non-covalent interaction analysis showed that the enantioselectivity is mainly caused by bond-rotation strain in the transition states of the deprotonation-aromatization step.
- Phosphoric acid catalysis,
- Theoretical calculations,
- Mechanism,
- Enantioselectivity
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