Synthesis and properties of derivatives of 2-deoxy-2-hydroxyimino-D-arabino-hexopyranosyl-L-cysteine and -thiophenol

3,4,6-Tri-O-acetyl-2-deoxy-2-hydroxyimino-alpha- and -beta-D-arabino-hexopyranosides of thiophenol (3-5) as well as the methyl ester of N-benzoyl-L-cysteine (6,7) have been synthesized by condensation of 3,4,6-tri-O-acetyl-2-deoxy-2-nitroso-alpha-D-glucopyranosyl chloride (1) with thiophenol and the L-cysteine derivative, respectively. The glycopyranosides of thiophenol were modified at C-2 and C-3 positions to afford thiophenol derivatives with 2-deoxy-2-hydroxyamino-alpha-D-glucopyranosyl (13,14), 3-azido-2,3-dideoxy-2-hydroxyimino-alpha-D-arabino- (8), beta-D-arabino- (10), and alpha-D-ribohexopyranosyl (9) structures. The conformation of the sugar residue and configuration at the anomeric center and of the hydroxyimino group were established on the basis of the H-1,C-13, N-15 NMR (DQF-COSY, TOCSY, NOESY, ROESY, HSQC, HMBC and HMBCN) spectrometric techniques and polarimetric data.