Simple Preparation of Dimethyldioxirane and Its Use as an Epoxidation Agent for the Transformation of Glycals to Glycosyl Phosphates

Dioxiranes represent a class of powerful oxygen-transfer reagents for the chemo-, regio- and stereoselective oxidation of a variety of substrates under mild conditions. ¹ The simplest compound of the dioxirane family, dimethyldioxirane (DMDO), can be obtained from the reaction of acetone with oxone (KHSO₅) in water under slightly basic conditions (Scheme 8.1). Intermolecular attack of the peroxymonosulfate on acetone is followed by an intramolecular nucleophilic substitution at the oxygen the initial attack originated from. Formation of acidic hydrogen sulfate is prevented by conducting the reaction in the presence of NaHCO₃.