Aliphatic allylamines are widely used for the synthesis of diverse building blocks for agrochemicals and pharmaceuticals; there is therefore considerable interest in developing versatile and direct routes to aliphatic allylamines using common chemical feedstocks—olefins and amines. However, examples of such coupling reactions remain limited. It is even more challenging to achieve this goal with precise site control. Here we report that the combination of a photocatalyst and cobaloxime enables site-selective amination of olefins with secondary alkyl amines to afford allylic amines, eliminating the need for oxidants. This method is compatible with a broad scope of olefins and can be extended to achieve a site- and diastereoselective amination of terpenes. Mechanistic studies disclose that the reaction proceeds via a cobaloxime-promoted hydrogen atom transfer pathway to afford the product that results from cleavage of the stronger, primary allylic C–H bonds over other weaker allylic C–H bond options.

脂肪族烯丙胺广泛用于合成农用化学品和药物的各种结构单元；因此，人们对使用常见的化学原料（烯烃和胺）开发脂肪族烯丙胺的通用和直接路线非常感兴趣。然而，这种偶联反应的例子仍然有限。通过精确的站点控制来实现这一目标更具挑战性。在这里，我们报告了光催化剂和钴肟的组合使烯烃与仲烷基胺进行位点选择性胺化以提供烯丙基胺，从而消除了对氧化剂的需求。该方法与广泛的烯烃相容，并且可以扩展以实现萜烯的位点和非对映选择性胺化。