Nature harnesses the unique properties of cysteinyl radical intermediates for a diverse range of essential biological transformations including DNA biosynthesis and repair, metabolism, and biological photochemistry. In parallel, the synthetic accessibility and redox chemistry of cysteinyl radicals renders them versatile reactive intermediates for use in a vast array of synthetic applications such as lipidation, glycosylation and fluorescent labelling of proteins, peptide macrocyclization and stapling, desulfurisation of peptides and proteins, and development of novel therapeutics. This review provides the reader with an overview of the role of cysteinyl radical intermediates in both chemical synthesis and biological systems, with a critical focus on mechanistic details. Direct insights from biological systems, where applied to chemical synthesis, are highlighted and potential avenues from nature which are yet to be explored synthetically are presented.

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化学合成和自然界中的半胱氨酰自由基

大自然利用半胱氨酰自由基中间体的独特特性进行各种基本的生物转化，包括 DNA 生物合成和修复、代谢和生物光化学。同时，半胱氨酰自由基的合成可及性和氧化还原化学使它们成为多种合成应用的多功能反应中间体，例如蛋白质的脂化、糖基化和荧光标记、肽大环化和缝合、肽和蛋白质的脱硫以及开发的新疗法。这篇综述为读者提供了半胱氨酰自由基中间体在化学合成和生物系统中的作用的概述，重点关注机械细节。来自生物系统的直接见解，应用于化学合成，