Cascade Synthesis of Pyrroles from Nitroarenes with Benign Reductants Using a Heterogeneous Cobalt Catalyst

A bifunctional 3d‐metal catalyst for the cascade synthesis of diverse pyrroles from nitroarenes is presented. The optimal catalytic system Co/NGr‐C@SiO(2)‐L is obtained by pyrolysis of a cobalt‐impregnated composite followed by subsequent selective leaching. In the presence of this material, (transfer) hydrogenation of easily available nitroarenes and subsequent Paal–Knorr/Clauson‐Kass condensation provides >40 pyrroles in good to high yields using dihydrogen, formic acid, or a CO/H(2)O mixture (WGSR conditions) as reductant. In addition to the favorable step economy, this straightforward domino process does not require any solvents or external co‐catalysts. The general synthetic utility of this methodology was demonstrated on a variety of functionalized substrates including the preparation of biologically active and pharmaceutically relevant compounds, for example, (+)‐Isamoltane.