When Light Meets Nitrogen-Centered Radicals: From Reagents to Catalysts

作者：Xiaoye Yu, Quanqing Zhao, Jun Chen, Jun Chen, Wen‐Jing Xiao, Jia‐Rong Chen, Jia‐Rong Chen · 发表于：Accounts of Chemical Research · 年份：2020 · DOI：10.1021/acs.accounts.0c00090 · 被引用次数：503 · 研究领域：Radical Photochemical Reactions、Sulfur-Based Synthesis Techniques、Catalytic C–H Functionalization Methods

Conspectus Nitrogen-centered radicals (NCRs) are a versatile class of highly reactive species that have a longer history than the classical carbon-based radicals in synthetic chemistry. Depending on the N-hybridization and substitution patterns, NCRs can serve as electrophiles or nucleophiles to undergo various radical transformations. Despite their power, progress in nitrogen-radical chemistry is still slow compared with the popularity of carbon radicals, and their considerable synthetic potential has been largely underexplored, which is, as concluded by Zard, mainly hampered by “a dearth of convenient access to these species and a lack of awareness pertaining to their reactivity”. Over the past decade, visible-light photoredox catalysis has been established as a powerful toolbox that synthetic chemists can use to generate a diverse range of radical intermediates from native organic functional groups via a single electron transfer process or energy transfer under mild reaction conditions. This catalytic strategy typically obviates the need for external stoichiometric activation reagents or toxic initiators and often enables traditionally inaccessible ionic chemical reactions. On the basis of our long-standing interest in nitrogen chemistry and catalysis, we have emphasized the use of visible-light photoredox catalysis as a tactic to discover and develop novel methods for generating NCRs in a controlled fashion and synthetic applications. In this Account, we describe our rece...