Waller Harry C, Gaunt Matthew J
Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom.
J Am Chem Soc. 2024 Sep 25;146(38):25894-25901. doi: 10.1021/jacs.4c08230. Epub 2024 Sep 16.
The α-amino-radical constitutes a versatile reactive intermediate that has been used to great effect in the synthesis of complex amine-containing products. Here, we report the development of a multicomponent photocatalytic platform enabling access to all-alkyl α-amino-radicals, exploiting the oxidative formation of silyl-radicals from commercially available tris(trimethylsilyl)silane. A key design element of the new process involves the role of silyl-radicals in generating α-amino-radicals from iminium ions as part of an oxidatively initiated photocatalytic radical chain process. This distinct activation mode is showcased by engaging the ensuing radicals in cross-radical coupling with persistent arene radical anions, enabling the arylation of in situ-generated all-alkyl iminium ions to furnish alkyl-substituted benzylamines.
α-氨基自由基是一种多功能的反应中间体，已在复杂含胺产物的合成中得到了广泛应用。在此，我们报道了一种多组分光催化平台的开发，该平台利用市售三（三甲基硅基）硅烷氧化生成硅基自由基，从而能够获得全烷基α-氨基自由基。新工艺的一个关键设计要素涉及硅基自由基在从亚胺离子生成α-氨基自由基过程中的作用，这是氧化引发的光催化自由基链反应的一部分。通过使生成的自由基与持久性芳烃自由基阴离子进行交叉自由基偶联，展示了这种独特的活化模式，从而实现原位生成的全烷基亚胺离子的芳基化反应，以提供烷基取代的苄胺。
