Substrate‐Controlled Regioselective Dibenzylation Reaction of 1,3‐Dicarbonyl Compounds: Access to <i>α</i> , <i>α</i> ‐Dibenzylated and <i>O</i> ‐Benzylated‐ <i>α</i> ‐Benzylated Products

A substrate‐controlled method for regioselective dibenzylation reaction of 1,3‐dicarbonyl compounds has been developed. The protocol employs readily available 1,3‐dicarbonyl compounds and benzyl bromides mediated by KOH at room temperature, which enables the divergent synthesis of α , α ‐dibenzylated products and O ‐benzylated‐ α ‐benzylated products with wide substrate scope and good functional group compatibility. Gram‐scale synthesis and further functionalization reaction demonstrate the potential practicability of this method in organic synthesis and drug development.