The synthesis of 2-azido C-glycosyl sugars

A short synthesis of 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-beta-D- glucopyranose and the corresponding alpha-glucosyl chloride from D-mannose.

Glycosyl phosphates, imidates, trifluoroacetates, chlorides, and bromides are converted into the respective glycosyl iodides by treatment with LiI or NaI in 1 M solutions of LiClO4 in CH2Cl2. Under these neutral conditions the reactive glycosyl iodides are activated, and react with different glycosyl acceptors to give O-glycosides in moderate yields, with the α-anomers predominating. The glycosylation reactions most probably proceed by the initial formation of β-configured glycosyl iodides from the α-configured precursors, and subsequent attack of the glycosyl acceptor on the equatorial iodide from the axial direction.

O‐Glycoside Synthesis with Glycosyl Iodides under Neutral Conditions in 1 M LiClO4 in CH2Cl2

Stereocontrolled synthesis of 2-azido and 2-N-acetylamino-2-deoxy-β-D-C-glycosides from the corresponding lactones

A straightforward route to N-acetyl-d-glucosamine-derived C-β-D-Glycosyl synthons

2-azido-2-deoxyhexopyranosyl cyanides

3,4,6-Tri-O-acetyl-2-azido-2-deoxyaldohexopyranosyl cyanides with the α-D-gluco, β-D-gluco, α-D-galacto, β-D-galacto, and α-D-manno configurations have been prepared and characterized. The synthetic sequence used was based on the free radical azidonitration of glycals sequence used was based on the free radical azidonitration of glycals developed by Lemieux and Ratcliffe [Can J. Chem., 57, 1244 (1979)]

R. W. Myers

Papers

2-azido-2-deoxyhexopyranosyl cyanides

2-Azido-2-deoxyhexopyranosyl Cyanides.