We introduce the first oxygen tolerant ultra-low volume (as low as 5 μL) photoinduced Cu-RDRP of a range of hydrophobic, hydrophilic and semi-fluorinated monomers.
Regioselective α,α-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 α,α-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.
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