Photoredox Catalysis Applications in Organometallics and Chemical Biology

Princeton University, Princeton NJ

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Abstract

Abstract. A central goal of our research program is to develop new platforms for the direct conversion of ubiquitous biomass feedstocks into fine chemical products. In recent years, these efforts have focused on the application of photoredox catalysis as a uniquely enabling paradigm in synthetic chemistry. The distinct features of photocatalysts, particularly their ability to readily effect single-electron transfer and thereby generate reactive open-shell radical species, have created new opportunities for reaction development, providing novel bond disconnections in synthetic sequences. The application of photoredox catalysis has been notably successful in the context of metallaphotoredox catalysis, which merges photocatalysis with transition-metal catalysis. Metallaphotoredox platforms enable non-traditional partners to participate in cross-coupling chemistry. Our group and others have used metallaphotoredox catalysis as a means to address many long-standing challenges in synthetic organic chemistry. This research proposal outlines new fields in which photoredox approaches have the potential to achieve significant impact. The objective of Research Program I is to develop new photoredox-mediated methodologies that proceed through a radical sorting / bimolecular homolytic substitution pathway. Successful execution of this program could theoretically allow selective coupling of virtually any two functional groups. In Research Program II, we propose to harness metallaphotoredox catalysis to develop new transformations that are not attainable via thermal pathways. Progress in this area would unlock new reactivity profiles, including carbenoid reactivity. Finally, Research Program III aims to make significant advances in our longstanding goal of converting feedstock chemicals to reactive radical intermediates. A focusing objective of this program is to establish alcohols as general cross-coupling handles for the installation of medicinally relevant functionality.