A Facile α-Glucuronidation Using Methyl 1,2,3,4-Tetra-O-acetyl-D-glucuronate as Glycosyl Donor

Abstract

Some terpenyl 2,3,4-tri-O-acetyl-α-D-glucuronide methyl esters were facilely synthesized from commercially available methyl 1,2,3,4-tetra-O-acetyl-β-D-glucuronate and terpenoid alcohols in the presence of bis(trifluoromethanesulfonyl)imide (Tf₂NH) in dichloromethane (DCM) in good yields. The predominant α-selectivity at the anomer position is caused via transition state in which the neighboring group participation of the methoxycarbonyl group at C-6 stabilizes the oxonium intermediate by forming ¹C₄ conformation. The intermediate accelerates the glucuronidation reaction despite the use of the acetyl group, which is not a good activating group in general glycosylation reactions, as the activating group.