Highly Selective Synthesis of Hydrazoarenes from Nitroarenes via Polystyrene-Supported Au-Nanoparticle-Catalyzed Reduction: Application to Azoarenes, Aminoarenes, and 4,4′-Diaminobiaryls

A selective synthesis of hydrazoarene from nitroarene and its application are reported. Using polystyrene (PS) resins as solid supports for Au nanoparticles (AuNPs), polystyrene-supported Au nanoparticles (AuNPs@PS) were synthesized and characterized. In the presence of AuNPs@PS (1.0 mol %) as a catalyst, nitroarenes afforded corresponding hydrazoarenes (up to 99%) with high selectivity (up to 100%) under mild reaction conditions (NaBH4, 50% aq. EtOH, and room temperature). Depending on the reaction conditions (the amount of NaBH4, the substituent of nitroarenes, and the sequential addition of HCl), nitroarenes were converted to corresponding azoarenes (up to 95%), aminoarenes (up to 99%), and 4,4′-diaminobiaryls (up to 99%). Our easily recyclable catalytic system using a solid-phase reaction vessel provides an attractive synthetic method in an eco-friendly and sustainable manner.