通过自由基接力伴侣实现醇的定向β-C-H 胺化反应。
Directed β C-H Amination of Alcohols via Radical Relay Chaperones.
机构信息
Department of Chemistry and Biochemistry, The Ohio State University , Columbus, Ohio 43210, United States.
出版信息
J Am Chem Soc. 2017 Aug 2;139(30):10204-10207. doi: 10.1021/jacs.7b05214. Epub 2017 Jul 25.
Abstract
A radical-mediated strategy for β C-H amination of alcohols has been developed. This approach employs a radical relay chaperone, which serves as a traceless director that facilitates selective C-H functionalization via 1,5-hydrogen atom transfer (HAT) and enables net incorporation of ammonia at the β carbon of alcohols. The chaperones presented herein enable direct access to imidate radicals, allowing their first use for H atom abstraction. A streamlined protocol enables rapid conversion of alcohols to their β-amino analogs (via in situ conversion of alcohols to imidates, directed C-H amination, and hydrolysis to NH). Mechanistic experiments indicate HAT is rate-limiting, whereas intramolecular amination is product- and stereo-determining.
摘要
已开发出一种用于醇的β C-H 胺化的自由基介导策略。该方法采用自由基接力陪伴物，作为无痕迹导向物，通过 1,5-氢原子转移 (HAT) 促进选择性 C-H 功能化，并使氨在醇的β碳上净结合。本文介绍的陪伴物可直接获得亚氨自由基，从而首次将其用于 H 原子的提取。简化的方案可实现醇快速转化为其β-氨基类似物（通过原位将醇转化为亚氨化物、定向 C-H 胺化以及水解为 NH）。机理实验表明 HAT 是速率限制步骤，而分子内胺化是产物和立体确定的步骤。
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