We now report that thiosugars can be obtained by rearrangement of thiocarbamates derivatives of monosaccharides in reaction with commercially available reagents in good yields. Thiosugars obtained by the rearrangement can be easily hydrolyzed, thus thiosaccharides unsubstituted in anomeric position can be obtained by this method as well. This thiocarbamates can be use in the orthogonal glycosylation.

In orthogonal glycosidation a range of glycosyl donors that bear different leaving groups (LG1/ LG2) and that can be selectively activated in the presence of each other, are utilized. A highly reactive donor is required for the first glycosidation in the orthogonal sequence¹. The O-glycosyl-N-allyl thiocarbamates (A) readily obtained from anomerically-unprotected sugars are very reactive glycosyl donors². They can be readily activated with bromine. On the other hand the S-glycosyl-N-allyl thiocarbamates (B) can be used as glycosyl acceptors. They can be activated with thiophilic reagents. The application this method to the synthesis of trisaccharides will be presented.

 Acknowledgement

Research studies part-financed by the European Union within the European Social Fund (POKL.04.01.01-00-114/09-00).

References

1) J. Pietruszka in Carbohydrates (H.M.L. Osborn Ed.) Academic Press, 2003, 219-239, 2) Barili P.L., Catelani G., D’Andrea F., De Rensis F., Falcini P. Carbohydrate Res. 1997, 298, 75-84; Ott A.J., Brackhagen M., Davtyan A., Nolting B., Boye H., Schoknecht A. and Vogel Ch. J. Carbohydrate Chemistry, 2001, 20, 611-636; Abbas S.A., Barlow J.J. and Matta K.L. Carbohydrate Res. 1981, 88, 51-60, Kasprzycka A., Ślusarczyk A. and Szeja W. Polish J. Chem. 2001, 75, 1303-1308; Kasprzycka A. and Szeja W. Polish J. Chem. 2005, 79, 329-333.

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