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An unprecedented dual photoredox/palladium-catalyzed iminyl-radical-mediated C–C bond cleavage and directed ortho C–H acylation of 2-arylpyridines by using oxime esters is described. Oxime esters can serve as efficient acyl sources through formation of the corresponding acyl radicals by photoredox-catalyzed iminyl-radical-mediated C–C bond cleavage. This redox-neutral protocol features excellent regioselectivity, a broad substrate scope, and good functional-group tolerance with respect to both components, giving a broad range of aryl ketones with generally good yields. [ABSTRACT FROM AUTHOR]

A copper-catalyzed regio-reversed asymmetric [3+2] cycloaddition of iminoesters with nitroolefins is disclosed for the first time. This method enables the facile synthesis of polysubstituted chiral pyrrolidines bearing at least one chiral quaternary center in high yields with excellent regio-, diastereo-, and enantioselectivity. The application of chiral P,S ligands and the unique effect of α-aryl groups on the iminoesters are key to the success of this method. The practicality and versatility of the reaction are also demonstrated., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)