A silver cleaver splits cyclic amines Carbon-carbon single bonds are fairly unreactive when they are not strained in a tight ring. Roque et al. now report that a silver salt can cleave C–C bonds in unstrained cyclic amines such as pyrrolidines and piperidines. Paired with an electrophilic fluorine source in aqueous solution, the silver first oxidizes the α carbon adjacent to the nitrogen. Ring-opening fluorination of the β carbon then proceeds by an apparent radical mechanism. The reaction offers a versatile means of introducing fluorine to structural motifs common in pharmaceutical research. Science, this issue p. 171 A silver-mediated reaction fluorinates saturated nitrogen heterocycles through carbon-carbon bond cleavage. Deconstructive functionalizations involving scission of carbon-carbon double bonds are well established. In contrast, unstrained C(sp3)–C(sp3) bond cleavage and functionalization have less precedent. Here we report the use of deconstructive fluorination to access mono- and difluorinated amine derivatives by C(sp3)–C(sp3) bond cleavage in saturated nitrogen heterocycles such as piperidines and pyrrolidines. Silver-mediated ring-opening fluorination using Selectfluor highlights a strategy for cyclic amine functionalization and late-stage skeletal diversification, establishing cyclic amines as synthons for amino alkyl radicals and providing synthetic routes to valuable building blocks.

中文翻译：

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通过碳-碳裂解环胺的解构氟化

银切割刀可以分裂环胺。当碳-碳单键没有在紧密的环中拉紧时，它们是相当不活泼的。罗克等人。现在报道银盐可以裂解无张力环胺（例如吡咯烷和哌啶）中的 C-C 键。银与水溶液中的亲电子氟源配对，首先氧化与氮相邻的α碳。然后通过明显的自由基机制进行β碳的开环氟化。该反应提供了一种将氟引入药物研究中常见结构基序的通用方法。科学，本期第 14 页。171 银介导的反应通过碳-碳键断裂氟化饱和氮杂环。涉及碳-碳双键断裂的解构性官能化已经很成熟。相比之下，无应变的 C(sp3)–C(sp3) 键断裂和功能化的先例较少。在这里，我们报告了使用解构氟化通过饱和氮杂环（​​例如哌啶和吡咯烷）中的 C(sp3)-C(sp3) 键断裂来获得单氟化胺和二氟化胺衍生物。使用 Selectflu 进行的银介导的开环氟化突出了环胺官能化和后期骨架多样化的策略，将环胺建立为氨基烷基自由基的合成子，并为有价值的结构单元提供合成路线。