Marat Ya. Karpeisky

New syntheses of 2′-C-methylnucleosides starting from d-glucose and d-ribose

Abstract Effective general methods have been developed for the synthesis of 2′-C-methylnucleosides starting from d -glucose and d -ribose. 3-O-benzyl-1,2-O-isopropylidene-3-C-methyl-α- d -allofuranose was prepared in 5 steps from d -glucose and converted into 1,2,3-tri-O-acetyl-2-C-methyl-5-O-p-methylbenzoyl- d -ribofuranose (5), the starting compound for nucleoside synthesis. Compound 5 was also synthesised from 2-C-hydroxymethyl-2,3-O-isopropylidene-5-O-trityl- d -ribofuranose, prepared in 3 steps from d -ribose. Condensation of 5 with the bis-trimethylsilyl derivatives of uracil, N4-benzoylcytosine, and N6-benzoyladenine in the presence of F3CSO3OSiMe3 followed by removal of the protecting acyl groups yielded the corresponding 2′-C-methylnucleosides.

Synthesis and properties of 3′-C-methylnucleosides and their phosphoric esters

Abstract 3′- C -Methyluridine and 3′- C -methylcytidine were synthesized in 11 steps starting from d -glucose. The conformation of 3′- C -methylnucleosides was studied in solution and in the crystal by using the techniques of c.d., 1 H-n.m.r. spectroscopy, and X-ray diffraction analysis. 3′- C -Methyluridine 2′,3′-cyclophosphate was prepared, and its hydrolysis with nucleases was studied. 3′- C -Methyluridine 5′- mono- and 5′-tri-phosphate were also synthesized.