N. K. Kochetkov

Synthesis of β-l-rhamnosyl pyrophosphate esters of thymidine, uridine, and 2′-deoxyuridine

1. We have carried out the chemical synthesis of some nucleoside 5′-(β-L-rhanmosyl pyrophosphates), derivatives of thymidine, uridine, and 2′-deoxyuridine. 2. We have developed a convenient modification of the pyrophosphate method for the synthesis of sugar nucleotides.

Chemistry of glycosyl phosphates and their derivatives

1. The fusion of theβ-tetraacetates of desoxy sugars with H3PO4 was used to obtain the 6, 4, and 3-desoxyglycosyl phosphates. 2. The optimum conditions for the separation of theα- andβ-anomers of the desoxyglycosyl phosphates were selected. 3. The previously unknown 2,3,6-tri-O-benzoyl-4-desoxy-α-methyl-D-xylo-hexopyranoside was obtained.

Analogs of coenzymes of carbohydrate metabolism: Communication 11. Synthesis of uridine diphosphate 6-deoxyglucose

Three analogs of adenosine diphosphate glucose with a modified nucleoside residue were synthesized: inosin diphosphate glucose,xanthosine diphosphate glucose, and 2′-deoxyadenosine triphosphate glucose.

Synthesis of thymidine 5′-(β-l-mannopyranosyl) and (4,6-dideoxy-l-lyxo-hexopyranosyl) pyrophosphates

We have prepared thymidine 5′-(β-L-mannopyranosyl pyrophosphate), thymidine 5′-(4,6-dideoxy-β-L-lyxohexopyranosyl pyrophosphate), and thymidine 5′-(4,6-dideoxy-α-L-lyxo-hexopyranosyl pyrophosphate), all analogs of thymidine 5′-(α-L-rhamnopyranosyl pyrophosphate), which is involved in the biosynthesis of the O-specific chains ofSalmonella lipopolysaccharides.

Chemistry of glycosyl phosphates and their derivatives Communication 4. Phosphorylation of benzoylated glycosyl acetates with phosphoric acid and synthesis of α- and Β-anomers of 4-o-methylsulfonyl-D-galactopyranosyl phosphate

1. Theα- andΒ-anomers of 4-O-methylsulfonyl-D-galactopyranosyl phosphate were synthesized by the fusion of 1-O-acetyl-2,3,6-tri-O-benzoyl-4-O-methylsulfonyl-Β-D-galactopyranose with anhydrous H3PO4. 2. TheΒ-anomers of glycosyl phosphates can predominate in the reaction products when glycosyl acetates, containing a benzoyl group at C-2, are phosphorylated. 3. It was shown that ion-exchange chromatography can be employed to separate the mixed anomers of protected glycosyl phosphates.