Catalytic Markovnikov-selective hydroamination of unactivated alkenes, in particular by using secondary amines as nucleophiles and/or in an intermolecular setting, remains a challenge. Here we address this problem by developing a cobalt-hydride-catalyzed hydroamination reaction based on a bimetallic redox-triggered oxidative amination pathway. This system enables the use of dioxygen as a sustainable oxidant that is compatible with free amines, while suppressing the facile radical oxygenation that leads to classical Drago-Mukaiyama oxidation. We demonstrate intra- and intermolecular formal addition of secondary amines across unactivated alkenes as well as vinylarenes at ambient temperature. The scope of this method also encompasses alternative nitrogen nucleophiles, such as sulfonamides, amides, and carbamates. Stoichiometric reactions of well-defined organocobalt complexes provide direct evidence for the proposed key amination process.

未活化烯烃的催化马尔科夫尼科夫选择性加氢胺化，特别是通过使用仲胺作为亲核试剂和/或在分子间环境中，仍然是一个挑战。在这里，我们通过开发基于双金属氧化还原触发的氧化胺化途径的钴氢化物催化的加氢胺化反应来解决这个问题。该系统能够使用分子氧作为与游离胺相容的可持续氧化剂，同时抑制导致经典 Drago-Mukaiyama 氧化的容易的自由基氧化。我们展示了仲胺在环境温度下跨未活化烯烃和乙烯基芳烃的分子内和分子间形式加成。该方法的范围还包括替代的含氮亲核试剂，例如磺胺类、酰胺类和氨基甲酸酯类。