Current‐Regulated Selective Nickel‐Catalyzed Electroreductive Cross‐Electrophile Carbonylation to β/γ‐Hydroxy Ketones

The nickel catalyzed multi-component cross-electrophile carbonylation which emerges as a powerful and efficient method for constructing diverse ketones has attracted increasing attention of organic chemists. However, the selectivity of this reaction poses a significant challenge. In this work, we have developed a current-regulated selective nickel-catalyzed electroreductive cross-electrophile carbonylation, which offers a direct convergent synthesis of β/γ-hydroxy ketones, which represent pivotal structural motifs found in numerous natural products, bioactive molecules, pharmaceutical compounds, and essential building blocks. A diverse range of multi-substituted β/γ-hydroxyketones can be accessed with high chemo- and regioselectivity from epoxides, aryl iodides, and a simple CO source (ClCO₂Pr). This electroreductive carbonylation strategy exhibits high functional group tolerance and can be applied in late-stage derivatization of drugs and natural products. Notably, chiral epoxides can be employed as reactants with chirality retention, enabling the synthesis of asymmetric β-hydroxy ketones. Our approach demonstrates a novel electrochemical selectivity-controlled strategy in multi-component cross-electrophile coupling.