Nickel/Copper Catalyzed C-C and C-N bond Formation Reactions to Forge sp3 Carbon Linkages

Identifier:  TDX:4264

Handle: https://hdl.handle.net/20.500.11797/TDX4264

Authors:  Lyu, Xinyang

Abstract:
Transition metal-catalyzed cross-coupling reactions have become indispensable tools for forging carbon-carbon and carbon-heteroatom bonds. These approaches have been widely applied to the preparation of biologically-relevant molecules and functional materials in both academic and industrial laboratories. Aimed at improving the applicability and practicality of these venerable reactions even further, chemists have been challenged to come up with new crosscoupling synthons that operate under ambient conditions, thus increasing the flexibility in synthetic design when accessing densely functionalized molecules. This Doctoral Thesis focuses on the development of new techniques to use ketones and unactivated halides in transition metal-catalyzed C-C bond and C-N bond cross-coupling reactions. First, a nickel/photoredox dual catalytic system for forging sp2–sp3 and sp3–sp3 bonds using ketone derived dihydroquinazolinones has been developed. This method is distinguished by its wide scope and broad application profile — including chemical diversification of advanced intermediates. Second, A copper-catalyzed C(sp3)-amination reaction of proaromatic dihydroquinazolinones with a variety of N-nucleophiles has been developed. Considering the prevalence of carbonyl compounds, this method might offer a new entry point to access C(sp3)–N architectures utilizing ketones as traceless synthons. Third, A copper-catalyzed C(sp3) amination of unactivated secondary alkyl iodides mediated by diaryliodonium salts has been described.