Deoxygenative Functionalization of Alcohols and Carbonyl Compounds via Electrochemical Reduction

Abstract Oxygen‐containing functional groups are prevalent motifs in natural products and feedstock chemicals, but direct methods for their deoxygenative transformation remain rare due to the difficult cleavage of the strong C–O bond. Here, we develop a general activation strategy that employs hydrosilanes as activating reagents for alcohols, carbonyls, and esters to afford a common silyl ether intermediate. Electrochemical reduction of the in situ generated silyl ether results in C–O cleavage to afford a carbanion, which reacts with a number of electrophiles for the construction of C–Si, C–B, C–Ge, and C–Sn bonds.