Theoretical Studies On The Mechanisms Of Rh And Ni Catalyzed C-H Activation Reactions

Quantum chemical calculation has been one fundamental tool for mechanisticinvestigation of organic reactions. In this thesis, several importanttransition-metal-catalyzed directing group-controlled C-H activation reactions wereinvestigated by performing density functional theory (DFT) calculation. Aftercomparing the energies of several possible reaction pathways, we found the detailedpathways which could explain phenomena existing in the reactions from theoreticalpoint of view. Moreover we wish these results could give theoretical guidance for thefurther catalytic reaction design. The whole thesis contains two research contents:(1) The mechanistic research of internal oxidant directing group-controlledRh(III)-catalyzed aromatic C-H functionalization. It is elucidated how the N-ORinternal oxidant controlled divergent reaction products of benzamide derivatives. Afterthe formation of7-membered rhodacycles, when N-OMe is involved, olefinationproduct was reached through a Rh(III)/Rh(I) catalytic cycle. However, for N-OPiv, theheterocycle product was reached through a Rh(III)/Rh(V) catalytic cycle.(2) The mechanistic research of Ni-catalyzed oxidative cycloaddition of alkyneand benzamide derivative containing2-pyridinylmethylamino group as a directinggroup for the formation of1(2H)-isoquinolone. The function of phosphine ligand was discovered.