Organic and Inorganic Strategies Targeting Carbon Heteroatom Bond Formation

440 pagesElectrochemical alkene diazidation offers an attractive strategy towards vicinal diamines due to the mild reaction conditions offered by oxidative electrochemistry and facile azide N3 to NH2 reduction methodologies. The electrochemical oxidation of TEMPO in the presence of N3— and an alkene was shown to electrochemically form azidooxygenated products alongside minor amounts of diazide. Diazide product formation was amplified alongside azidooxygenation suppression through the synthesis of a sterically congested catalyst CHAMPO. CHAMPO was able to successfully catalyze the formation of diazides across a variety of alkene types and substrates featuring oxidatively sensitive functional groups. Organometallic catalysts offer an alternative route to carbon heteroatom bond formation as unlike purely organic catalysts, the multiple oxidation states accessible through redox manipulation of a metal center allows access to otherwise inaccessible reaction paradigms. Carbazole-based PNP pincer complexes of Co were synthesized and reacted with RN3 to furnish Co-imidos (Co=NR) which have been invoked as key intermediates in C—H amination and C=C aziridination. Upon full characterization, the competency of Co=NR towards C—N bond formation was investigated. A second generation PNP pincer complex was synthesized to incorporate binding of a main-group metal with the hypothesis that transition metal main-group cooperativity would allow for activation and binding of ligands atypical for monometallic systems. Heterobimetallic systems of E—TM (E = Gallium and Indium, M = Cobalt and Nickel) were synthesized and characterized using SXRD and their activity towards Nitrogen oxyanion (NO3— and (NO2—) binding was investigated