title: Theoretical Investigation of Regioselectivity and Stereoselectivity in AIBN/HSnBu3-Mediated Radical Cyclization of N-(2-Iodo-4,6-dimethylphenyl)-N,2-dimethyl-(2E)-butenamide.
abstract: 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.
authors.affiliation: Key Laboratory of Functional Inorganic Material Chemistry (Ministry of Education of China) and School of Chemistry and Materials Science, Heilongjiang University , Harbin 150080, P. R. China.
authors.forename: Bai-Jian
authors.initials: BJ
authors.lastname: Li
authors.affiliation: Key Laboratory of Functional Inorganic Material Chemistry (Ministry of Education of China) and School of Chemistry and Materials Science, Heilongjiang University , Harbin 150080, P. R. China.
authors.forename: Hua
authors.initials: H
authors.lastname: Zhong
authors.affiliation: Key Laboratory of Functional Inorganic Material Chemistry (Ministry of Education of China) and School of Chemistry and Materials Science, Heilongjiang University , Harbin 150080, P. R. China.
authors.forename: Hai-Tao
authors.identifier: 0000-0003-3764-9201
authors.initials: HT
authors.lastname: Yu