Study On The Mechanism Of Chiral Transfer Of Ortho-anilide

In this thesis,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 was further utilized 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.