A Reusable Co Catalyst for the Selective Hydrogenation of Functionalized Nitroarenes and the Direct Synthesis of Imines and Benzimidazoles from Nitroarenes and Aldehydes

The use of abundantly available transition metals in reactions that have been preferentially mediated by rare noble metals, for example, hydrogenations, is a desirable aim in catalysis and an attractive strategy for element conservation. The observation of novel selectivity patterns with such inexpensive metal catalysts is especially appealing. Herein, we report a novel, robust, and reusable cobalt catalyst that permits the selective hydrogenation of nitroarenes in the presence of highly hydrogenation‐sensitive functional groups, as well as the direct synthesis of imines from nitroarenes and aldehydes or ketones in the presence of such substituents. Furthermore, we introduce the first base‐metal‐mediated direct synthesis of benzimidazoles from nitroarenes and aldehydes. Functional groups that are easy to hydrogenate are again well tolerated.