Recent progress in photocatalytic reactions involving the excitation of electron-primed catalysts

Takashi Koike
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Abstract

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.

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电子引发催化剂的光催化反应研究进展
开壳类植物因其独特的理化性质和高活性而备受关注。在过去的十年中,光氧化还原催化(PRC)已成为自由基反应的一种强有力的策略。近年来,光催化在合成有机化学中也引起了广泛的关注,其中包括由原位光或电化学电子转移产生的开壳催化物质的激发。这些系统可以实现在光催化剂基态或通过光催化剂的简单激发难以实现的氧化还原电位。在这篇综述文章中,我们讨论了高还原性有机光催化剂(OPC)体系的最新进展,该体系涉及电子引发的催化物质的光激发,可以从事光化学(conPET:连续光诱导电子转移)或电化学(e-PRC:电化学介导的光氧化还原催化)。我们相信,从氧化还原电位的角度来看,扩大催化剂的氧化还原窗口以激活惰性底物将改善合理的反应设计,并且使用复杂的OPC系统将有望实现难以捉摸的分子转化。
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