We report intra- and intermolecular γ-amino C(sp³)–H functionalization of aliphatic amines using a vinylsulfone-based HAT (hydrogen atom transfer) auxiliary and a triple catalysis, which is composed of photoredox, cobalt, and Brønsted acid catalysts under visible light irradiation. The process accomplishes four elementary steps: (i) electrophilic carbon-centered radical formation on the HAT auxiliary via MHAT (metal hydride hydrogen atom transfer) reaction, (ii) generation of a γ-amino carbon-centered radical through 1,6-HAT reaction, (iii) single-electron oxidation to carbocation equivalents, and (iv) nucleophilic substitution with internal or external nucleophiles. As a result, this γ-amino C(sp³)–H functionalization afforded γ-amino-functionalized products, such as azetidines, 1,3-diamine, and 1,3-aminoalcohol derivatives.

中文翻译：

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通过光驱动三重催化对脂肪胺进行 γ-氨基 C(sp3)–H 官能化

我们报告了使用乙烯基砜基 HAT（氢原子转移）辅助剂和三重催化作用对脂肪胺进行分子内和分子间 γ-氨基 C(sp ³ )–H 官能化，该三重催化由光氧化还原、钴和布朗斯台德酸催化剂组成。可见光照射。该过程完成四个基本步骤：(i) 通过 MHAT（金属氢化物氢原子转移）反应在 HAT 辅助剂上形成亲电碳中心自由基，(ii) 通过 1,6-HAT 生成 γ-氨基碳中心自由基反应，（iii）单电子氧化成碳阳离子当量，以及（iv）用内部或外部亲核试剂进行亲核取代。结果，这种γ-氨基C(sp ³ )–H官能化提供了γ-氨基官能化产物，例如氮杂环丁烷、1,3-二胺和1,3-氨基醇衍生物。