Regioselective alpha,alpha-difunctionalization adjacent to a ketone is a significant synthetic challenge. Here, we present a solution to this problem through the transition-metal-free coupling of esters with geminal bis(boron) compounds. This forms an alpha,alpha-bis(enolate) equivalent which can be trapped with electrophiles including alkyl halides and fluorinating agents. This presents an efficient, convergent synthetic strategy for the synthesis of unsymmetrical blocked ketones.