铜催化、氮导向的远端 C(sp 3 )-H 功能化反应合成氮杂环庚烷。
Copper-Catalyzed, N-Directed Distal C(sp)-H Functionalization toward Azepanes.
机构信息
Jiangsu Key Laboratory of Neuropsychiatric Diseases and Department of Medicinal Chemistry, College of Pharmaceutical Sciences, Soochow University, 199 Ren-Ai Road, Suzhou, Jiangsu 215123, People's Republic of China.
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
出版信息
Org Lett. 2022 Oct 28;24(42):7796-7800. doi: 10.1021/acs.orglett.2c03135. Epub 2022 Oct 20.
We herein report a copper-catalyzed formal [5 + 2] aza-annulation of -fluorosulfonamides and 1,3-dienes/1,3-enynes for synthesis of structurally diverse alkene/alkyne-containing azepanes. The reaction features selective functionalization of distal unactivated C(sp)-H bonds and a broad substrate scope, thus allowing the late-stage modification of pharmaceuticals and natural products. A radical mechanism involving 1,5-hydrogen atom transfer of N-radicals, facile coupling of alkyl radicals with 1,3-dienes/1,3-enynes, and the construction of azepane motifs via C-N bond formation is proposed.
我们在此报告了一种铜催化的 -氟磺酰胺和 1,3-二烯/1,3-烯炔的形式 [5 + 2] 氮杂环加成反应，用于合成结构多样的含烯烃/炔烃的氮杂环庚烷。该反应具有对远端未活化 C(sp)-H 键的选择性功能化和广泛的底物范围，因此允许对药物和天然产物进行晚期修饰。提出了一种涉及 N-自由基的 1,5-氢原子转移、烷基自由基与 1,3-二烯/1,3-烯炔的易偶联以及通过 C-N 键形成构建氮杂环庚烷结构的自由基机理。
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