A synthetic route to 9-(polyhydroxyalkyl)purines.
Mercuric-ion promoted condensation of 6-chloropurine with acetylated dimethyl dithioacetals of D-ribose and D-arabinose in nitromethane afforded a separable mixture of 1'(S)-2,3,4,5-tetra-O-acetyl-1-(6-chloropurin-9-yl)-1-S-methyl-1-thio-D-ribitol (4) and its 1'(R) diastereomer, and the corresponding 1'(R)-arabinitol analogue (5); the structure of 4 was confirmed by X-ray crystallography. Desulfurization of 4 and 5 by tributylstannane in toluene gave 2,3,4,5-tetra-O-acetyl-1-(6-chloropurin-9-yl)-1-deoxy-D-ribitol (7) and the arabinitol analogue 8, convertible by the action of thiourea into the 1,6-dihydro-6-thioxopurin-9-yl analogues 9 and 10, which on deacetylation furnished the corresponding acyclic-sugar nucleosides 11 and 12.
Horton
Derek
D
Department of Chemistry, American University, 4400 Massachusetts Avenue, NW, Washington, DC 20016, USA. carbchm@american.edu
Thomas
Sheela
S
Gallucci
Judith
J
D001089:Arabinose / Q000031:analogs & derivatives / Q000138:chemical synthesis / Q000737:chemistry; D002236:Carbohydrate Conformation; D018360:Crystallography, X-Ray; D008279:Magnetic Resonance Imaging; D008968:Molecular Conformation; D015394:Molecular Structure; D009705:Nucleosides / Q000138:chemical synthesis / Q000737:chemistry; D011687:Purines / Q000138:chemical synthesis* / Q000737:chemistry; D012266:Ribose / Q000031:analogs & derivatives / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism
D009705:Nucleosides; D011687:Purines; D012266:Ribose; D001089:Arabinose