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Abstract:
Over the past decade, a novel photochemical concept termed Ligand-to-Metal Charge Transfer (LMCT) has emerged, which diverges from the classic photocatalysis and has brought many exciting opportunities in organic synthesis. LMCT chemistry leverages the in-situ formed light-absorbing metal complexes for redox processes, which simplifies the photochemical reaction conditions and complements classic photoredox catalysis. This dissertation probes the application of photoinduced ligand-to-copper charge transfer in the decarboxylative functionalization and C–H functionalization of aromatic compounds. The focus is on decarboxylative hydroxylation of benzoic acids, decarboxylative sulfoximination of benzoic acids, and C–H sulfoximination of arenes, all of which were previously unachievable transformations. The accomplishment of these synthetic challenges is rooted in the unique mechanistic characteristics of the copper-LMCT platform. Copper is pivotal in the charge transfer process for the facile generation of radical intermediates and crucial in modulating the reactivity of these radicals, directing them towards the desired reaction pathway.
The application of Ligand-to-Metal Charge Transfer (LMCT) chemistry in organic synthesis is still in its nascent stage. However, the findings presented in this dissertation underscore its substantial potential for resolving long-standing challenges in the field of chemistry, thereby serving as an enabling tool for future advancements.
