Stereoselective synthesis of 4'-selenonucleosides using the Pummerer glycosylation reaction.
The syntheses of four selenonucleosides, namely 4'-beta-selenoadenosine, -cytidine, -thymidine, and -uridine are described. Commercially available D-ribonolactone was converted to the key intermediate 1,4-anhydro-4-seleno-D-ribitol in seven steps in overall excellent yield. Oxidation of the seleno-d-ribitol with MCPBA gave a single diastereomeric selenoxide in excellent yield, which upon Pummerer reaction in the presence of silylated purine or pyrimidine bases gave stereoselectively the corresponding 4'-beta-selenonucleosides. The stereochemistry at the anomeric center was determined by means of 1D-NOE experiments.
Jayakanthan
Kumarasamy
K
Department of Chemistry, Simon Fraser University, Burnaby, BC, Canada.
Johnston
Blair D
BD
Pinto
B Mario
BM
D000241:Adenosine / Q000031:analogs & derivatives* / Q000138:chemical synthesis; D003562:Cytidine / Q000031:analogs & derivatives / Q000138:chemical synthesis; D006031:Glycosylation; D009705:Nucleosides / Q000138:chemical synthesis*; D016566:Organoselenium Compounds / Q000138:chemical synthesis*; D012643:Selenium / Q000737:chemistry*; D013237:Stereoisomerism; D013936:Thymidine / Q000031:analogs & derivatives / Q000138:chemical synthesis; D014529:Uridine / Q000031:analogs & derivatives / Q000138:chemical synthesis
C531224:4'-selenoadenosine; C528351:4'-selenocytidine; C531225:4'-selenothymidine; C528350:4'-selenouridine; D009705:Nucleosides; D016566:Organoselenium Compounds; D003562:Cytidine; D012643:Selenium; D000241:Adenosine; D013936:Thymidine; D014529:Uridine