Theoretical Investigation of Regioselectivity and Stereoselectivity in AIBN/HSnBu3-Mediated Radical Cyclization of N-(2-Iodo-4,6-dimethylphenyl)-N,2-dimethyl-(2E)-butenamide
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- 作者：Bai-jian Li ; Hua Zhong ; Hai-tao Yu
- 刊名：Journal of Physical Chemistry B
- 出版年：2016
- 出版时间：December 22, 2016
- 年：2016
- 卷：120
- 期：50
- 页码：12950-12958
- 全文大小：817K
- ISSN：1520-5207
文摘
In this study, we employed the density functional method to simulate AIBN/HSnBu3-mediated radical cyclizations with different axially chiral conformers of N-(2-iodo-4,6-dimethylphenyl)-N,2-dimethyl-(2E)-butenamide as substrates. We constructed a reaction potential energy profile using the Gibbs free energies of the located stationary points. The thermodynamic and kinetic data of the profile were further used to evaluate the regioselectivity, stereoselectivity, and product distribution of the cyclizations. Additionally, we compared the present HSnBu3-mediated radical cyclization with the experimentally available Heck reaction and found that such a radical cyclization can convert (M,Z) and (P,Z) o-iodoanilide substrates to centrally chiral products with high chirality transfer. The goal of this study was to estimate the practicality of theoretically predicting the memory of chirality in such radical cyclizations. The present results can provide a strategy from a theoretical viewpoint for experimentally synthesizing highly stereoselective carbocyclic and heterocyclic compounds using radical cyclization methods.