Gold‐Catalyzed Direct Hydrogenative Coupling of Nitroarenes To Synthesize Aromatic Azo Compounds

The azo linkage is a prominent chemical motif which has found numerous applications in materials science, pharmaceuticals, and agrochemicals. Described herein is a sustainable heterogeneous‐gold‐catalyzed synthesis of azo arenes. Available nitroarenes are deoxygenated and linked selectively by the formation of N?N bonds using molecular H₂ without any external additives. As a result of a unique and remarkable synergy between the metal and support, a facile surface‐mediated condensation of nitroso and hydroxylamine intermediates is enabled, and the desired transformation proceeds in a highly selective manner under mild reaction conditions. The protocol tolerates a large variety of functional groups and offers a general and versatile method for the environmentally friendly synthesis of symmetric or asymmetric aromatic azo compounds.