Molybdenum-Catalyzed Reductive Ortho-Allylation of Nitroarenes with 1,3-Dienes

Abstract

The direct catalytic reductive functionalization of nitroarenes to produce amines with enhanced properties continues to attract attention for both academic and industrial synthesis. However, most previous reports on the reductive functionalization of nitroarenes were based on C-NAr bond formation; the reductive functionalization on the aryl group for the synthesis of functionalized anilines has been scarcely reported. Here, we report a reductive ortho-allylation of nitroarenes with 1,3-dienes via molybdenum catalysis. Various ortho-allyl anilines were regioselectively produced in favorable yields from easily accessible precursor materials. This work represents a unique instance of the reductive functionalization of nitroarenes which forms a C–C bond on the aryl group to synthesize functionalized anilines. Notable features of this work include: (1) the reductive functionalization of nitroarenes on the aryl group, (2) high stereoconvergent synthesis, wherein the mixtures of E/Z isomers of 1,3-dienes selectively yield E-isomer products, and (3) broad substrate scopes, accompanied by favorable yields and selectivity.