Homogeneous Dearomative Hydrogenation with a Co/P4N2 Catalyst: A Nucleophilic Approach.

Arene hydrogenation is the most straightforward method to prepare carbo‐ and heterocycles. However, the high resonance energy prevents aromatic substrates from hydrogenation. Herein the homogeneous, nucleophilic hydrogenation of less electron‐rich arenes and heteroarenes is reported. The Co(P4N2)H species that has been demonstrated to be a strong hydride donor could deliver a hydride ion to the cyano (hetero)arene substrates. Deuterium labeling experiments supported a Michael‐type reaction pathway. Theoretical analyses have been conducted to investigate the hydricity of the catalytically active CoH species and the electrophilicity of the arene substrates. An outlook for the synthesis of more challenging substituted benzenes was proposed based on the in silico modification of the CoH species. [ABSTRACT FROM AUTHOR]