Citation: Zhu Lei, Wang Zheyuan, Liu Song, Zhang Tao, Yang Zhen, Bai Ruopeng, Lan Yu. Theoretical prediction on the reactivity of the Co-mediated intramolecular Pauson-Khand reaction for constructing bicyclo-skeletons in natural products[J]. Chinese Chemical Letters, ;2019, 30(4): 889-894. doi: 10.1016/j.cclet.2019.03.024 shu

Theoretical prediction on the reactivity of the Co-mediated intramolecular Pauson-Khand reaction for constructing bicyclo-skeletons in natural products

Zhu Lei ^a,1 ,
Wang Zheyuan ^a,1 ,
Liu Song ^a ,
Zhang Tao ^a ,
Yang Zhen ^c,*, ,
Bai Ruopeng ^a,**, ,
Lan Yu ^a,b,*,

a.
School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing 400030, China
b.
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, China
c.
Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, China

zyang@pku.edu.cn

ruopeng@cqu.edu.cn

lanyu@cqu.edu.cn

Received Date: 23 January 2019
Revised Date: 8 March 2019
Accepted Date: 11 March 2019
Available Online: 15 April 2019

Figures(4)

The Co₂(CO)₈-mediated intramolecular Pauson-Khand reaction is an efficient approach for constructing polycyclic skeletons. Recently, some of us reported a series of this type reactions involving stericallyhindered enynes for synthesizing natural products with reasonable reaction rates and yields. However, the reason for the high reactivity of the reaction remains unclear. We employed density functional theory calculations to clarify the mechanism and reactivity for this reaction. In contrast with chain olefin reactants, CO insertion is considered to be the rate-determining step for the overall Pauson-Khand reaction of cyclooctene derivatives. The reduced activation free energy for the alkene insertion step is attributed to:i) the electron-withdrawing group in close proximity to the C-C triple bond enhancing the reactivity of the alkyne moiety; ii) lower steric hindrance during alkene insertion when using the cyclooctene derivative. The effect of the substituent on the Co₂(CO)₈-mediated intramolecular Pauson-Khand reaction was then investigated. Internal alkenes exhibit lower reactivity than terminal alkenes because of the steric hindrance introduced by the substituted group. The cis internal alkene exhibits higher reactivity than the trans internal alkene. An ester group in close proximity to the C -C triple bond significantly enhances the reactivity.
- Pauson-Khand reaction,
- Bicyclo-skeletons,
- DFT calculations,
- Mechanism,
- Reactivity
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