Catalytic ceric ammonium nitrate mediated synthesis of 2-deoxy-1-thioglycosides

Synthesis of 2-deoxy-1-thioglycosides from glycals, mediated by catalytic amounts of ceric ammonium nitrate is reported. Glycosylation reactions of the thioglycosides with both aglycosyl and glycosyl acceptors afford α-anomeric glycosides exclusively. Synthesis of 2-deoxy-1-thioglycosides from glycals, mediated by catalytic amounts of ceric ammonium nitrate is reported. Apart from the 2-deoxy-1-thioglycosides, formation of the 2,3-unsaturated enose, corresponding to the Ferrier product, is also observed, especially for the glucal substrates. A radical oxocarbenium ion and a thiolate intermediates are most likely to mediate the reaction. Upon synthesis of 2-deoxy-1-thioglycosides, few representative glycosylation reactions with both aglycosyl and glycosyl acceptors were performed and α-anomeric 2-deoxy glycosides were obtained exclusively.