Stibine-catalyzed selective conversion of nitroarenes to hydroxylanilines through deoxygenation and hydroboration processes

Abstract

We accomplish the synthesis of hydroxylanilines, which usually serve as transient intermediates in nitro reduction, directly from nitroarenes by employing HBpin as the reductant and a simple stibine (nBu₃Sb) as the catalyst, demonstrating the unique chemoselectivity of antimony redox catalysis. Mechanistic investigations reveal that the transformation proceeds through relay deoxygenation and hydroboration processes via distinct Sb^III/Sb^V cycling, highlighting the diverse redox reactivity of antimony catalysts.