D-Arabinose-based synthesis of homo-C-d4T and homo-C-thymidine.
2,3,5-Tri-O-benzyl-D-arabinofuranosyl halides (chloride, bromide) were reacted with AllMgBr, MeMgBr, and VinMgBr to furnish anomeric mixtures of the C-glycosyl products. The factors that influenced the beta/alpha ratio are discussed. The alpha,beta-C-vinyl derivative was transformed into 1-deoxy-1-C-hydroxymethyl-beta- and -alpha-D-arabinofuranoses (2,5-anhydro-D-glucitol and -mannitol, respectively), separable after isopropylidenation step. 2,5-Anhydro-1,3-O-isopropylidene-D-glucitol was converted into 2,5-anhydro-6-O-triphenylmethyl-D-erythro-hex-3,4-enitol and 2,5-anhydro-4,6-di-O-benzoyl-3-deoxy-D-ribo-hexitol, which were coupled with N-3-benzoylthymine under the Mitsunobu conditions to furnish two analogs of nucleosides with a -CH(2)- insert between sugar moieties and thymine.
Doboszewski
Bogdan
B
Departmento de Química, Universidade Federal Rural de Pernambuco, Recife, Pernambuco, Brazil. bdoboszewski@hotmail.com
D001089:Arabinose / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D013237:Stereoisomerism; D013936:Thymidine / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000737:chemistry
D001089:Arabinose; D013936:Thymidine