Study On The Mechanism Of The Synthesis Of O-iodoaniline Deiodinated Ring

In this thesis,we employed density functional theory and numerical simulation methods to investigate the mechanism of the intramolecular radical cyclization reactions of orthohalo-N-acryloylanilides bearing N-alkyl substituents,namely,methyl,ethyl,and isopropyl.We calculated the half-lives of substrates and constructed Gibbs free energy potential energy profiles using the energies of optimized stationary points.We established kinetic differential equations for the elementary reaction pathways in potential energy profiles as a function of time and further performed numeric simulations for these equation using the theoretically computed kinetic and thermodynamic data and rate constants to obtain the time-dependent concentration distributions of reactants,intermediates and products.By using those results,we in detail discussed reaction mechanism,involving radical atropisomerization,cyclization,neophyl-like rearrangements,and reductions,which can be used to reveal the preferred reaction channels,product branching ratio,and chiral transfer ratio.Furthermore,the temperaturedependent regio-and stereoselectivity were investigated quantitatively.Additionally,we also determined the ratio of the ee of products to that of reactants and the dependence of the ratio on temperature under enantiomeric reaction condition.Thus,the ortho-halo-Nacryloylanilides with large enough N-alkyl substituents are promising candidates for constructing nitrogen-containing heterocyclic compounds in high regio-and stereoselectivity via the radical cyclization strategy.The results and conclusions provided an insight into an approach access to chiral transfer ratio and into the selection of substrates that can be used to high regio-or stereoselectively syntheze nitrogencontaining heterocyclic compounds using the intramolecular radical cyclization method.