Molybdenum-Catalyzed Reductive <i>Ortho</i>-Allylation of Nitroarenes with 1,3-Dienes

The direct catalytic reductive functionalization\nof nitroarenes\nto produce amines with enhanced properties continues to attract attention\nfor both academic and industrial synthesis. However, most previous\nreports on the reductive functionalization of nitroarenes were based\non C-NAr bond formation; the reductive functionalization on the aryl\ngroup for the synthesis of functionalized anilines has been scarcely\nreported. Here, we report a reductive <i>ortho</i>-allylation\nof nitroarenes with 1,3-dienes via molybdenum catalysis. Various <i>ortho</i>-allyl anilines were regioselectively produced in favorable\nyields from easily accessible precursor materials. This work represents\na unique instance of the reductive functionalization of nitroarenes\nwhich forms a C–C bond on the aryl group to synthesize functionalized\nanilines. Notable features of this work include: (1) the reductive\nfunctionalization of nitroarenes on the aryl group, (2) high stereoconvergent\nsynthesis, wherein the mixtures of <i>E/Z</i> isomers of\n1,3-dienes selectively yield <i>E</i>-isomer products, and\n(3) broad substrate scopes, accompanied by favorable yields and selectivity.