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Ni-Catalyzed 1,2-Acyl Migration Reactions Triggered by C–C Bond Activation of Ketones

A Ni-catalyzed 1,2-acyl migration triggered by C–C bond cleavage was developed. The process of 1,2-acyl migration followed by olefin isomerization provides a convenient access to α,β-unsaturated ketones, which are well-known building blocks in organic synthesis. Experimental and computational studies show that the selective β-hydride elimination and Ni-hydride reinsertion play an essential role in this reaction.