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Open-shell species are attracting significant attention owing to their unique physicochemical properties and highly reactive characteristics. Over the past decade, photoredox catalysis (PRC) has emerged as a powerful strategy for radical reactions. Recently, photocatalysis involving the excitation of open-shell catalytic species generated from in situ photo- or electrochemical electron transfer has also attracted significant attention in synthetic organic chemistry. These systems can achieve redox potentials that are difficult to achieve in the ground state of the photocatalyst or by simple excitation of the photocatalyst. In this review article, we discuss recent advancements in highly reducing organic photocatalyst (OPC) systems involving the photoexcitation of electron-primed catalytic species, which can be engaged in photochemically (conPET: consecutive photoinduced electron transfer) or electrochemically (e-PRC: electrochemically mediated photoredox catalysis). We believe that expanding the redox windows of catalysts to activate inert substrates from the viewpoint of redox potential will improve rational reaction design, and the use of sophisticated OPC systems will be promising for achieving elusive molecular transformations.