Sterically congested α-tertiary primary amines are ubiquitous substructures in pharmaceutical and agrochemical agents yet are challenging to access. Herein, a straightforward photoredox-catalyzed access to structurally diverse α,α,α-trisubstituted primary amines from denitrogenative alkylarylation or dialkylation of vinyl azides with NHPI esters and cyanoarenes or aryl aldehydes has been developed. The use of vinyl azides as a precursor of primary amines was enabled by the dual role of Hantzsch ester to form electron donor-acceptor (EDA) complexes and to serve as a sacrificial reductant. This strategy provides a modular synthesis of α-tertiary primary amines, including unprotected 1,2-amino alcohols, from simple materials with excellent functional group tolerance. The synthetic applicability of this method was demonstrated by streamlined access to 2,2-disubstituted tetrahydroquinolines. Preliminary investigations support two parallel reductive photocatalytic cycles allowing for the denitrogenative alkylarylation or dialkylation of vinyl azides via decarboxylative radical addition followed by hetero-radical cross-coupling between α-amino radicals and aryl anion radicals or ketyl anion radicals.

中文翻译：

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光诱导脱氮烷芳基化/二烷基化从乙烯基叠氮化物合成 α-叔伯胺和 1,2-氨基醇

空间拥挤的 α-叔伯胺是药物和农用化学品中普遍存在的亚结构，但难以获得。在此，开发了一种直接的光氧化还原催化途径，从乙烯基叠氮化物与 NHPI 酯和氰基芳烃或芳基醛的脱氮烷基芳基化或二烷基化反应中获得结构多样的 α,α,α-三取代伯胺。Hantzsch 酯的双重作用使乙烯基叠氮化物用作伯胺的前体，形成电子供体-受体 (EDA) 复合物并用作牺牲还原剂。该策略提供了 α-叔伯胺（包括未保护的 1,2-氨基醇）的模块化合成，由具有优异官能团耐受性的简单材料制成。通过简化获得 2,2-二取代四氢喹啉的方法证明了该方法的合成适用性。初步研究支持两个平行的还原光催化循环，允许乙烯基叠氮化物通过脱羧自由基加成进行脱氮烷基芳基化或二烷基化，然后是 α-氨基自由基和芳基阴离子自由基或羰基阴离子自由基之间的杂自由基交叉偶联。