Switchable Mechanical-Force-Induced Selective Reduction of Nitroarenes via Piezoelectric Perovskite Materials

Abstract

Nitroarenes, as a class of environmentally hazardous pollutants with significant ecological and health risks, present critical challenges in their efficient transformation into high-value-added compounds. While reductive amination reactions have attracted considerable attention due to their remarkable reliability and functional group tolerance, they still face substantial challenges in chemoselectivity control, catalytic system economy, and mild reaction conditions. This study innovatively develops a mechanocatalytic strategy with switchable selectivity, achieving controlled synthesis of both anilines and azoxybenzenes through precise regulation of nitroarene reduction pathways. Employing cost-effective, environmentally benign tet-BaTiO₃ as a mechanocatalyst, we demonstrate the first mechanodriven nitroarene reduction system, establishing a versatile platform for synthesizing these two important compound classes. Mechanistic investigations reveal that the strategic modulation of proton doner and catalyst redox potential serves as the pivotal mechanism governing reaction pathway selection. Through systematic optimization of key parameters including mechanocatalyst selection, proton donors, and additives, we achieved target product yields ranging from moderate to excellent. Comprehensive mechanistic studies elucidate the reaction pathways and operational principles underlying this precisely controlled mechanocatalytic system.