Synthesis of 5-Methyluridine and Its 5'-Mercapto-, 2-Amino-, and 4',5'-Unsatured Analogues

Article abstract of DOI:10.1002/hlca.19800630808

The stereospecific cis-hydroxylation of 1-(2,3-dideoxy-β-D-glyceropent-2-enofuranosyl)thymine (1) into 1-β-D-ribofuranosylthymine (2) by osmium tetroxyde is described.Treatment of 2',3'-O,O-isopropylidene-5-methyl-2,5'-anhydrouridine (8) with hydrogen sulfide or methanolic ammonia afforded 5'-deoxy-2',3'-O,O-isopropylidene-5'-mercapto-5-methyluridine (9) and 2',3'-O,O-isopropylidene-5-methyl-isocytidine (10), respectively.The action of ethanolic potassium hydroxide on 5'-deoxy-5'-iodo-2',3'-O,O-isopropylidene-5-methyluridine (7) gave rise to the corresponding 1-(5-deoxy-β-D-erythropent-4-enofuranosyl)5-methyluracil (13) and 2-O-ethyl-5-methyluridine (14).The hydrogenation of 2 and its 2',3'-O,O-isopropylidene derivative 4 over 5percent Rh/AL2O3 as catalyst generated diastereoisomers of corresponding 5-methyl-5,6-dihydrouridine (17 and 18).