Duke University, Department of Chemistry, Box 90346, Durham, North Carolina 27708-0354, United States.
Chem Rev. 2022 Jan 26;122(2):2353-2428. doi: 10.1021/acs.chemrev.1c00444. Epub 2021 Oct 8.
For more than 70 years, nitrogen-centered radicals have been recognized as potent synthetic intermediates. This review is a survey designed for use by chemists engaged in target-oriented synthesis. This review summarizes the recent paradigm shift in access to and application of -centered radicals enabled by visible-light photocatalysis. This shift broadens and streamlines approaches to many small molecules because visible-light photocatalysis conditions are mild. Explicit attention is paid to innovative advances in N-X bonds as radical precursors, where X = Cl, N, S, O, and H. For clarity, key mechanistic data is noted, where available. Synthetic applications and limitations are summarized to illuminate the tremendous utility of photocatalytically generated nitrogen-centered radicals.
70 多年来,氮中心自由基一直被认为是有效的合成中间体。本综述旨在为从事目标导向合成的化学家提供参考。本综述总结了可见光光催化在获得和应用氮中心自由基方面最近的范式转变。这种转变拓宽并简化了许多小分子的方法,因为可见光光催化条件温和。特别关注 N-X 键作为自由基前体的创新进展,其中 X = Cl、N、S、O 和 H。为了清晰起见,在有可用的情况下,还注意到了关键的机理数据。综述了合成应用和局限性,以阐明光催化生成的氮中心自由基的巨大用途。