Expeditious syntheses of sugar-modified nucleosides and collections thereof exploiting furan-, pyrrole-, and thiophene-based siloxy dienes.
A series of individual sugar-modified pyrimidine nucleosides including enantiomerically enriched 2',3'-dideoxynucleosides 14a-c (alpha and beta anomers of L- and D-series), 2',3'-dideoxy-4'-thionucleosides 21a-c (alpha and beta anomers of L- and D-series), and 2',3'-dideoxy-4'-azanucleosides 28a-c (beta anomers of L- and D-series) were synthesized, with uniform chemistry and high stereochemical efficiency, exploiting a triad of versatile heterocyclic siloxy dienes, namely, 2-(tert-butyldimethylsiloxy)furan (TBSOF), 2-(tert-butyldimethylsiloxy)thiophene (TBSOT), and N-(tert-butoxycarbonyl)-2-(tert-butyldimethylsiloxy)pyrrole (TBSOP). The synthetic procedure advantageously used both enantiomers of glyceraldehyde acetonide (D-1 and L-1) as sources of chirality and as synthetic equivalents of the formyl cation. The outlined chemistry also allowed for the rapid assemblage of a 30-member collection of racemic nucleosides (D,L-L) as well as one 15-member ensemble of chiral analogues (L-L), along with some related sublibraries.
Rassu
G
G
Instituto per l'Applicazione delle Tecniche Chimiche Avanzate del CNR, Sassari, Italy.
Zanardi
F
F
Battistini
L
L
Gaetani
E
E
Casiraghi
G
G
D005663:Furans / Q000138:chemical synthesis*; D009705:Nucleosides / Q000138:chemical synthesis*; D011758:Pyrroles / Q000138:chemical synthesis*; D017655:Silicon Compounds / Q000138:chemical synthesis*; D013237:Stereoisomerism; D013876:Thiophenes / Q000138:chemical synthesis*
D005663:Furans; D009705:Nucleosides; D011758:Pyrroles; D017655:Silicon Compounds; D013876:Thiophenes