Transition-Metal Catalyzed C-H Bond Amination from Aryl Azide

This thesis describes transition metal catalyzed benzylic and aliphatic C--H amination reaction by employing aryl azides as the nitrogen source, with the generation of indoline. Additionly, Rh(II) carboxylate promoting disubtituted indole formation from beta, beta-disubstituted styryl azide is discussed afterwards.;Chapter one briefly introduce a variety of C--H bond functionalization including borylation, silylation and amination. Among them, amination has been widely discussed: intermolecular and intramolecular C--H bond amination are described respectively. Subsequently, Iridium complexes and Rh(II) carboxylate used to promote C--H bond functionalization are well studied. Finally, two examples are shown to demonstrate the application of transition metal catalyzed C--H bond amination.;Chapter two discloses benzylic C--H bond amination catalyzed by iridium complex, producing 2-arylindoline. This reaction features low catalyst loading and mild condition. However, the methodology is limited on benzylic C--H bond and lead to no reaction if electron donationg group attached on the aryl azide. Mechanism study implies that an electrophilic iridium nitrenoid (14) is generated in the reaction.;Chapter three discribes thermally robust Rh2(esp)2 could catalyze the aliphatic amination transformation without requiring electron poor environment on the aryl azide. Due to the decomposition of other metal catalysts at high temperature, no reaction was observed by using other rhodium carboxylate, and iridium, iron, copper catalysts. To improve the isolated yield of the amination, Boc2O was added to the reaction mixture to protect the resulting indoline. N-atom transfer mechanism was proposed to explained the reaction activities.;Chapter four investigates Rhodium-catalyzed synthesis of 2,3-disubstituted indoles from beta,beta-disubstituted styryl azide with controlling the selectivity of migration of one of the beta- substituents. We discovers that aryl group migrates faster than alkyl group and more electron rich group prefers participate in migration. The migratorial aptitude suggests that a phenonium ion is reactive intermediate.