Mass spectrometric studies of anomeric glycopyranosyl azides.

We studied the mass spectrometric behaviour of peracetylated and underivatized anomeric hexopyranosyl azides and 5-thioglucopyranosyl azides by means of different mass spectrometric techniques. The unstable molecular ions fragment predominantly by losing either N3 radical or N2 molecule. Loss of N2 molecule and the protonation of the derived nitrene were characteristic of the studied compounds. The presence of BF3.Et2O in the ion source is favorable for producing the protonated nitrene form. The protonated nitrene shows a new type of ring expansion rearrangement. The abundances of the [M + H - N2]+ ion makes it possible to identify the anomeric configuration of the azido group.

Identification and synthesis of a trisaccharide produced from lactose by transgalactosylation.

Enzymatic transgalactosylation of lactose by means of Streptococcus thermophilus, subspecies DN-001065, led to a mixture of D-galactose (approximately 4%), D-glucose (approximately 15%), lactose (approximately 51%), minor disaccharides (6%), trisaccharides (approximately 20%) and tetrasaccharides (3%). The major trisaccharide (approximately 16%) was identified by NMR spectroscopy and chemical synthesis as being the known beta-D-galactopyranosyl-(1-->3)-beta-D-galactopyranosyl-(1-->4)-D-glucos e (3'-beta-D-galactopyranosyl-lactose). It was purified from a mixture of peracetylated oligosaccharides by column chromatography followed by deacetylation. For the first time, 3'-beta-D-galactopyranosyl-lactose has been obtained on the 1 g scale, by resorting to simple techniques and equipment. NMR spectra have been unambiguously assigned.

An improved synthesis of an umbelliferyl 5-thioxylopyranoside, precursor of the antithrombotic drug Iliparcil.

4-Ethyl-2-oxo-2H-1-benzopyran-7-yl 2,3,4-tri-O-acetyl-5-thio-beta-D-xylopyranoside, a synthetic intermediate of the orally active antithrombotic compound Iliparcil, has been prepared in 44-47% isolated yield. Different conditions were used for the glycosylation of 4-ethyl-2H-7-hydroxy-1-benzopyran-2-one 6 applying 2,3,4-tri-O-acetyl-5-thio-D-xylopyranosyl bromide (2), the analogous beta-chloride 3 or the alpha-trichloroacetimidate 5 as donors. With halides 2 and 3, the reaction was carried out in the presence of ZnO-ZnCl2 or ZnO alone. Both promoters are cheap, safe and therefore compatible with large-scale industrial processes.