Enzymatic regioselective levulinylation of 2'-deoxyribonucleosides and 2'-o-methylribonucleosides.
The levulinyl-protected nucleosides are key building blocks for the solution-phase synthesis of oligonucleotides. Short and efficient syntheses of 3'- and 5'-O-levulinylated 2'-deoxyribonucleosides and 2'-O-methylribonucleosides have been developed from the corresponding nucleosides by enzyme-catalyzed regioselective acylation in organic solvents or from 3',5'-di-O-levulinyl derivatives by regioselective enzymatic hydrolysis. Lipase-mediated levulinylation of various nucleosides has been accomplished with acetonoxime levulinate as an acyl donor. Use of immobilized Pseudomonas cepacia lipase (PSL-C) has furnished 3'-O-levulinylated 2'-deoxyribonucleosides in excellent yields. Similarly, Candida antarctica lipase B (CAL-B) has provided 5'-O-levulinylated nucleosides in high yields. 3'-O-Levulinylated 2'-deoxyribonucleosides and 2'-O-methylribonucleosides were prepared via selective hydrolysis of 3',5'-di-O-levulinate esters using CAL-B.
Lavandera
Iván
I
Universidad de Oviedo, Oviedo, Spain.
García
Javier
J
Fernández
Susana
S
Ferrero
Miguel
M
Gotor
Vicente
V
Sanghvi
Yogesh S
YS
D016956:Burkholderia cepacia / Q000201:enzymology; D002175:Candida / Q000201:enzymology; D002384:Catalysis; D002855:Chromatography, Thin Layer; D006868:Hydrolysis; D007982:Levulinic Acids / Q000737:chemistry*; D008049:Lipase / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D012263:Ribonucleosides / Q000138:chemical synthesis / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization
D007982:Levulinic Acids; D012263:Ribonucleosides; D008049:Lipase; C032246:levulinic acid