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 achieving chemoselectivity control, catalytic system economy, and mild reaction conditions. This study innovatively developed a mechanocatalytic strategy with switchable selectivity, achieving the controlled synthesis of both anilines and azoxybenzenes through the precise regulation of nitroarene-reduction pathways. Employing cost-effective, environmentally benign tet-BaTiO₃ as a mechanocatalyst, we demonstrated the first mechano-driven nitroarene-reduction system, establishing a versatile platform for synthesizing these two important compound classes. Mechanistic investigations revealed that strategic modulation of the proton donor and catalyst redox potential served as the pivotal mechanism governing the reaction pathway selection. Through the systematic optimization of key parameters, including the mechanocatalyst, proton donors, and additives, we achieved target product yields ranging from moderate to excellent. Comprehensive mechanistic studies elucidated the reaction pathways and operational principles underlying this precisely controlled mechanocatalytic system.