Sp ~ 2 Carbon Free Radicals Build N Heterocyclic Compounds Ring Mechanism Research

In this thesis, intramolecular radical cyclization mechanism of SP~2-carbon arylswere investigated by using of DFT methods. N-methyl-N-(N-methylindoacyl)aniline-2-yl radical, N-methyl-N-furanacyl-aniline-2-yl radical, and N-methyl-N-(N-methyl-N-phenylcarbamoyl)aniline-2-yl radical were selected as target systems. Theoreticalinverstigation results provided corresponding reaction potential energy surfaces andreaction pathways of aryl radical intramolecular cyclizations. Furthermore, theregioselectivity and reaction mechanism were also explained by the contribution ofkinetic and thermodynamic effects, changes of structural parameters of key species inradical cyclizations, and corresponding orbital interaction energies. The results showedthat the present theoretical methods can correctly predict the mechanism ofintramolecular radical cyclizations, intermediate geometries, product distributions, intrinsic barriers, the thermodynamics contribution to the dynamics, and the changes inorbitals of electronic attack reactions. By the methods and technologies, one cancorrectly predict the reaction selectivity and trend of intramolecular radical cyclizations,and the given theoretical information can directly provide availably experimental targetsfor organic systhesis chemists.