Co‐Catalyzed Synthesis of Primary Amines via Reductive Amination employing Hydrogen under very mild Conditions

Nanostructured and reusable 3d‐metal catalysts that operate with high activity and selectivity in important chemical reactions are highly desirable. Here, a cobalt catalyst was developed for the synthesis of primary amines via reductive amination employing hydrogen as the reducing agent and easy‐to‐handle ammonia, dissolved in water, as the nitrogen source. The catalyst operates under very mild conditions (1.5 mol% catalyst loading, 50 °C and 10 bar H(2) pressure) and outperforms commercially available noble metal catalysts (Pd, Pt, Ru, Rh, Ir). A broad scope and a very good functional group tolerance were observed. The key for the high activity seemed to be the used support: an N‐doped amorphous carbon material with small and turbostratically disordered graphitic domains, which is microporous with a bimodal size distribution and with basic NH functionalities in the pores.