1187662-65-2Relevant articles and documents
2,3-Anhydrosugars in glycoside bond synthesis: Mechanism of 2-deoxy-2-thioaryl glycoside formation
Hou, Dianjie,Taha, Hashem A.,Lowary, Todd L.
supporting information; experimental part, p. 12937 - 12948 (2009/12/07)
A series of investigations probing the mechanism of the 2,3-anhydrosugar migration - glycosylation reaction were performed using a thioglycoside with the D-lyxo stereochemistry as the substrate. Among the work reported are the results of quantum mechanical calculations, NMR studies, the measurement of α-deuterium kinetic isotope effects, and the synthesis of a series of substrate analogues. All studies point to a consistent finding: that the reaction proceeds through an oxocarbenium ion intermediate, not an episulfonium ion as previously suggested. It is proposed that the high stereoselectivity of the reaction arises from a preferred "inside attack" of the nucleophile onto the oxocarbenium ion intermediate.
