Naturally produced halogenated compounds are ubiquitous across all domains of life where they perform a multitude of biological functions and adopt a diversity of chemical structures. Accordingly, a diverse collection of enzyme catalysts to install and remove halogens from organic scaffolds has evolved in nature. Accounting for the different chemical properties of the four halogen atoms (fluorine, chlorine, bromine, and iodine) and the diversity and chemical reactivity of their organic substrates, enzymes performing biosynthetic and degradative halogenation chemistry utilize numerous mechanistic strategies involving oxidation, reduction, and substitution. Biosynthetic halogenation reactions range from simple aromatic substitutions to stereoselective C–H functionalizations on remote carbon centers and can initiate the formation of simple to complex ring structures. Dehalogenating enzymes, on the other hand, are best known for removing halogen atoms from man-made organohalogens, yet also function naturally, albeit rarely, in metabolic pathways. This review details the scope and mechanism of nature’s halogenation and dehalogenation enzymatic strategies, highlights gaps in our understanding, and posits where new advances in the field might arise in the near future.

中文翻译：

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酶促卤化和脱卤反应：普遍且机制多样

天然产生的卤代化合物在生命的各个领域中普遍存在，它们执行多种生物功能并采用多种化学结构。因此，自然界中已经进化出多种用于在有机支架上安装和去除卤素的酶催化剂。考虑到四种卤素原子（氟、氯、溴和碘）的不同化学性质及其有机底物的多样性和化学反应性，进行生物合成和降解卤化化学的酶利用多种涉及氧化、还原和取代的机械策略。生物合成卤化反应的范围从简单的芳香族取代到远程碳中心上的立体选择性 C-H 官能化，并且可以引发简单到复杂的环结构的形成。另一方面，脱卤酶最出名的是从人造有机卤素中去除卤素原子，但它也在代谢途径中自然发挥作用，尽管很少。这篇综述详细介绍了自然界卤化和脱卤酶策略的范围和机制，强调了我们理解中的差距，并假设该领域在不久的将来可能会出现新的进展。