Thiosugars. I. Synthesis of Derivatives of 2-Amino-2-deoxy-1-thio-D-glucose¹

Abstract

A range of derivatives of 2-a~o-2-deoxy-~-thio-~-glucose, with removable blocking substituents at the amino and thiol groups, has been synthesized by condensation of amino sugar glycosyl halides with thiourea, with potassium thiolacetate, or with potassium ethylxanthate.

Stereoselective Synthesis of 3‐Deoxy‐4‐S‐(1→4)‐Thiodisaccharides and Their Inhibitory Activities Towards β‐Glycoside Hydrolases

“…(2S,6S)-6-Acetoxymethyl-2-(2-propyloxy)-2H-pyran-3(6H)-one (1), readily prepared from d-galactose via 2-acetoxy-3,4,6-tri-O-acetyl-d-galactal, [13] was employed as a Michael acceptor of 2,3,4,6-tetra-O-acetyl-1-thio-β-d-galactopyranose [21] (2). The addition of 2 to 1 proceeded rapidly at 0°C (30 min) in a CH 2 Cl 2 solution containing a catalytic amount of triethylamine (Et 3 N).…”

“…[11] Furthermore, the configuration of the C-4 stereocenter of the thiodisaccharides is opposite to that produced by similar reactions applied to levoglucosenone. [9,10] The Michael addition of 2,3,4,6-tetra-O-acetyl-1-thio-β-d-glucopyranose [21] (3) to 1 was also studied. Under the reaction conditions employed previously, coupling of 1 with 3 led to the thiodisaccharide 5 in 81 % yield.…”

The synthesis of uridine diphosphate N-acetylhexosamines and uridine 5′-(2-acetamido-2-deoxy-α-D-mannopyranosyluronic acid diphosphate)

“…The preparation of the catalyst is time-consuming and did not give a catalyst of consistent quality. Therefore, compound 15 was selectively oxidized, in the presence of commercially available 10% platinum-on-carbon (Fluka-Tridorn), by bubbling oxygen into a mixture of 15 in aqueous sodium hydrogen carbonate solution for 7 h at 75"C, to give uridine 5'-(2-acetamido-2-deoxy-a-D-rnannopyranosyluronic acid diphosphate) (20) in 20% yield.…”

“…These compounds are therefore frequently required for biosynthetic investigations, and good methods of synthesis, both The chemical methods available for preparing nucleoside diphosphate sugars, especially the hexosamine derivatives (3), are often inconvenient and time-consuming, especially in the purification stages, and yields are variable. This is particularly true for uridine 5'-(2-acetamido-2-deoxy-WDmannopyranosyluronic acid diphosphate) (20) (4) which was required by us for the study of the biosynthesis of the antigenic polysaccharide in the cell wall of Micrococcus lysodeikticus (5,6). Furthermore, when compound 20 was prepared previously (4), it was characterized indirectly, and its properties were not recorded.…”

New adriamycin analogs. Synthesis and antitumor activity of 14-substituted 7-O-(3,4-di-O-acetyl-2,6-dideoxy-.ALPHA.-l-lyxo-hexopyranosyl)daunomycinones.

“…The azide 7 showed characteristic IR absorption at 2120 cm-1 and the 13C signal of C-14 in 7 (at 54. For consolidation of all signal assignments for the glycon portion of compounds 7-10, the 1H and 13C NMR spectra of a suitable model compound, methyl 3,4-di-O-acetyl-2,6-dideoxy-a-L-1)•xohexopyranosidel3> (11) were recorded, and the corresponding spectral data are incorporated in Tables 1 and 2.…”