Dehydroxylative Alkylation of α‐Hydroxy Carboxylic Acid Derivatives via a Spin‐Center Shift

A strategically distinct dehydroxylative alkylation reaction of α‐hydroxy carboxylic acid derivatives with alkenes is developed. The reaction starts with the attack of a 4‐dimethylaminopyridine (DMAP)‐boryl radical to the carbonyl oxygen atom, followed by a spin‐center shift (SCS) to trigger the C−O bond scission. The resulting α‐carbonyl radicals couple with a wide range of alkenes to furnish various alkylated products. This strategy allows for the efficient conversion of a wide array of α‐hydroxy amides and esters derived from several biomass molecules and natural products to value‐added compounds. Experimental and computational studies verified the reaction mechanism. A DMAP‐boryl radical breaks the α‐C−O bond of α‐hydroxy amides and esters via a spin‐center shift (SCS) mechanism, enabling the facile conversion of abundantly available and/or naturally occurring α‐hydroxy acids to value‐added alkylated products.