Enzymatic regioselective levulinylation of 2'-deoxyribonucleosides and 2'-o-methylribonucleosides

Curr Protoc Nucleic Acid Chem. 2005 Jul:Chapter 2:Unit 2.11. doi: 10.1002/0471142700.nc0211s21.

Abstract

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.

MeSH terms

  • Burkholderia cepacia / enzymology
  • Candida / enzymology
  • Catalysis
  • Chromatography, Thin Layer
  • Hydrolysis
  • Levulinic Acids / chemistry*
  • Lipase / chemistry*
  • Magnetic Resonance Spectroscopy
  • Ribonucleosides / chemical synthesis
  • Ribonucleosides / chemistry*
  • Spectrometry, Mass, Electrospray Ionization

Substances

  • Levulinic Acids
  • Ribonucleosides
  • Lipase
  • levulinic acid