P<sup>III</sup>/P<sup>V</sup>═O-Catalyzed Intermolecular N–N Bond Formation: Cross-Selective Reductive Coupling of Nitroarenes and Anilines
Gen Li, Steven P. Miller, Alexander T. Radosevich
Abstract
An organophosphorus-catalyzed method for the synthesis of unsymmetrical hydrazines by cross-selective intermolecular N–N reductive coupling is reported. This method employs a small ring phosphacycle (phosphetane) catalyst together with hydrosilane as the terminal reductant to drive reductive coupling of nitroarenes and anilines with good chemoselectivity and functional group tolerance. Mechanistic investigations support an autotandem catalytic reaction cascade in which the organophosphorus catalyst drives two sequential and mechanistically distinct reduction events via PIII/PV═O cycling in order to furnish the target N–N bond.
Topics & Concepts
ChemistryChemoselectivityCatalysisIntermolecular forceCoupling reactionReductive eliminationCombinatorial chemistryMedicinal chemistryRing (chemistry)Organic chemistryMoleculeCatalytic C–H Functionalization MethodsAsymmetric Hydrogenation and CatalysisCatalytic Cross-Coupling Reactions