Dehydroxylative Alkylation of α‐Hydroxy Carboxylic Acid Derivatives via a Spin‐Center Shift
Tianyu Peng, Zheyuan Xu, Feng‐Lian Zhang, Bin Li, Wenping Xu, Yao Fu, Yi‐Feng Wang
Abstract
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.