Department of Chemistry, University of California, Berkeley, CA 94720, USA.
Science. 2018 Jul 13;361(6398):171-174. doi: 10.1126/science.aat6365.
Deconstructive functionalizations involving scission of carbon-carbon double bonds are well established. In contrast, unstrained C(sp)-C(sp) bond cleavage and functionalization have less precedent. Here we report the use of deconstructive fluorination to access mono- and difluorinated amine derivatives by C(sp)-C(sp) 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.
涉及碳-碳双键断裂的解构性功能化反应已经得到了很好的建立。相比之下，未受应变的 C(sp)-C(sp)键断裂和功能化反应则先例较少。在这里，我们报告了使用解构性氟化反应，通过饱和氮杂环如哌啶和吡咯烷中的 C(sp)-C(sp)键断裂，来获得单氟和二氟胺衍生物。使用 Selectfluor 的银介导的开环氟化反应突出了一种环状胺官能化和后期骨架多样化的策略，将环状胺确立为氨基烷基自由基的前体，并提供了有价值的构建块的合成途径。
