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光氧化还原催化的黎明。

Dawn of photoredox catalysis.

作者信息

Akita Munetaka

机构信息

Institute of Science Tokyo (former Tokyo Institute of Technology).

出版信息

Proc Jpn Acad Ser B Phys Biol Sci. 2025;101(5):274-301. doi: 10.2183/pjab.101.019.

Abstract

Photoredox catalysis, which facilitates organic transformations under visible-light irradiation, including sunlight, has garnered considerable attention as a cornerstone of green chemistry. Since the early days of this field around 2010, the author's group has made substantial contributions to its advancement. This review article provides a concise overview of the history and fundamental principles of photoredox catalysis, along with highlights of the achievements by the author's group. Although colorless organic compounds cannot be directly activated by visible light, photo-excited colored catalysts, with their two half-occupied frontier orbitals, play dual roles via electron transfer processes with organic substrates. The hole in the lower-energy orbital functions as a single-electron oxidant, whereas the electron in the higher-energy orbital acts as a single-electron reductant, enabling the formation of reactive radical intermediates from diverse organic compounds, including colorless ones. The discussion will focus on the key transformations developed by the author's group, including bimetallic photocatalysis, fluoroalkylation, and catalysis in aqueous media.

摘要

光氧化还原催化能够在可见光照射(包括阳光)下促进有机转化,作为绿色化学的基石已备受关注。自2010年左右该领域早期以来,作者所在团队为其发展做出了重大贡献。这篇综述文章简要概述了光氧化还原催化的历史和基本原理,以及作者所在团队取得的成就亮点。尽管无色有机化合物不能被可见光直接活化,但光激发的有色催化剂凭借其两个半占据的前沿轨道,通过与有机底物的电子转移过程发挥双重作用。较低能量轨道中的空穴充当单电子氧化剂,而较高能量轨道中的电子充当单电子还原剂,从而能够从包括无色化合物在内的各种有机化合物中形成反应性自由基中间体。讨论将聚焦于作者所在团队开发的关键转化反应,包括双金属光催化、氟烷基化以及在水介质中的催化反应。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5cd6/12332418/995f828d92da/pjab-101-274-g001.jpg

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