Simple synthesis of glycosylthiols and thioglycosides by rearrangement of O-glycosyl thionocarbamates

•Thionocarbamates undergo O,S-rearrangement when treated with acid.•Glycosyl N-methyl thiolcarbamates were applied to the synthesis of heteroaryl thioglycosides.•Both anomers of aromatic heteroaryl glycosides were prepared.•Synthesized thioglycosides can serve as stable glycosyl acceptors.

The synthesis of thioglycosides has been achieved in a high yielding process employing thionocarbamates prepared from protected reducing sugars and N-alkyl isothiocyanate in the presence of a non-nucleophilic base (K2CO3). In the key step of the synthesis, thionocarbamates were treated with Lewis acid (TMSOTf) to give O,S-rearrangement products that were applied to the synthesis of both anomers of heteroaryl thioglycosides.

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