New photochemical methods for catalytic radical processes

Identifier:  TDX:4322

Handle: https://hdl.handle.net/20.500.11797/TDX4322

Authors:  Zhou, Wei

Abstract:
The work carried out in this doctoral thesis has highlighted how different photochemical activation manifolds can be used to generate radicals and design new catalytic processes. In chapter 11, it was shown that dithiocarbamates and xanthogenates were used as catalytic donors in the formation of photoactive electron donor-acceptor (EDA) complexes with a variety of radical precursors. Excitation with visible light riggered the generation of open-shell intermediates under mild conditions, including non-stabilized carbon radicals and nitrogen-centered radica Is. The modular nature of the organocatalysts offered a versatile EDA complex catalytic platform for developing mechanistically distinct radical reactions, including redox neutral and net-reductive processes. Mechanistic investigations supported the hypothesis that a closed catalytic cycle is operational, highlighting the ability of the organic catalysts to turnover and iteratively drive each catalytic cycle. Chapter 111 detailed that tetrachlorophthalimide-based catalysts can actas effective and general acceptors for EDA complex activation.