Cobalt-Catalyzed Acceptorless Dehydrogenation of Primary Amines to Nitriles

作者：Haitao Tian, Cai‐Yun Ding, Rong‐Zhen Liao, Man Li, Conghui Tang · 发表于：Journal of the American Chemical Society · 年份：2024 · DOI：10.1021/jacs.4c00493 · 被引用次数：38 · 研究领域：Asymmetric Hydrogenation and Catalysis、Carbon dioxide utilization in catalysis、Metal-Organic Frameworks: Synthesis and Applications

The direct double dehydrogenation from primary amines to nitriles without an oxidant or hydrogen acceptor is both intriguing and challenging. In this paper, we describe a non-noble metal catalyst capable of realizing such a transformation with high efficiency. A cobalt-centered N, N- bidentate complex was designed and employed as a metal–ligand cooperative dehydrogenation catalyst. Detailed kinetic studies, control experiments, and DFT calculations revealed the crucial hydride transfer, proton transfer, and hydrogen evolution processes. Finally, a tandem outer-sphere/inner-sphere mechanism was proposed for the dehydrogenation of amines to nitriles through an imine intermediate.