Oxidative Nucleophilic Substitution of Hydrogen in Nitroarenes with Carbanions of Protected Serine and Threonine Esters

Abstract

AbstractThe reactions of carbanions of protected serine and threonine esters with nitroarenes were studied. The main process involves the addition of the carbanions to the para position of the nitroarenes, which is occupied by a hydrogen atom, to form σH adducts that are subsequently oxidized by 2,3‐dichloro‐5,6‐dicyanobenzoquinone to give p‐nitroaryl derivatives of the protected serine and threonine. Oxidation of the σH adducts with dimethyldioxirane resulted in the formation of the corresponding p‐hydroxyaryl derivatives of these amino acids. Addition of the carbanions of the protected threonine ester is a highly stereoselective process controlled by the second chiral center of threonine.