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

作者：Tianyu Peng, Zheyuan Xu, Feng‐Lian Zhang, Bin Li, Wenping Xu, Yao Fu, Yi‐Feng Wang · 发表于：Angewandte Chemie International Edition · 年份：2022 · DOI：10.1002/anie.202201329 · 被引用次数：36 · 研究领域：Cyclopropane Reaction Mechanisms、Catalytic C–H Functionalization Methods、Synthetic Organic Chemistry Methods

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.