NFSI‐TEMPO Catalysed Stereoselective Synthesis of 2‐Deoxyglycosides from Glycals

2‐deoxyglycosides are prominent constituents of diverse naturally occurring glycans and are known to participate in crucial biological pathways. We herein demonstrate NFSI‐TEMPO as an efficient organocatalyst for the formation of 2‐deoxy‐α‐glycosides from glycals. For the first time a catalytic behaviour of NFSI‐TEMPO combination has been observed. The reaction conditions have been found suitable for the generation of glycosides from commercial alcohols, amino acid, sterol, phenols and monosaccharide derived alcohols. Broad range of protecting groups on both glycal and glycosyl acceptors as well as alcohols of varied reactivity were found to be compatible for the generation of 2‐deoxy‐α‐glycosides in moderate to good yields. The synthetic potential of the newly established transformation was illustrated by application in trisaccharide synthesis and gram‐scale reaction.