Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States.
Org Lett. 2022 Apr 15;24(14):2762-2766. doi: 10.1021/acs.orglett.2c00869. Epub 2022 Apr 4.
The -activating substituents typically encountered in C-H amination chemistry are challenging to remove and have limited scope for synthetic elaboration. Here, we demonstrate that -benzylaminopyridinium species provide a platform for synthetic elaboration via reductive N-N bond activation to unveil electrophilic -centered radicals. These reactive intermediates can be trapped either via anti-Markovnikov olefin carboamination to provide access to tetrahydroisoquinolines or via aza-Rubottom chemistry with silyl enol ethers to provide α-amino ketones.
在 C-H 胺化化学中，常见的 - 活化取代基难以去除，且在合成中可进一步修饰的范围有限。在这里，我们证明 - 苄基氨基吡啶鎓物种通过还原 N-N 键活化提供了一个用于合成修饰的平台，从而揭示出亲电性的 - 中心自由基。这些反应中间体可以通过反马氏规则的烯烃碳氨化来捕获，从而提供四氢异喹啉；或者通过与硅基烯醇醚的氮杂-鲁本妥化学来捕获，从而提供 α- 氨基酮。
