Enzymatic Regioselective Levulinylation of 2′‐Deoxyribonucleosides and 2′‐ O ‐Methylribonucleosides

• Published in: Current Protocols in Nucleic Acid Chemistry
• Main Authors: Lavandera, Iván, García, Javier, Fernández, Susana, Ferrero, Miguel, Gotor, Vicente, Sanghvi, Yogesh S.
• Format: Article in Journal/Newspaper
• Language: English
• Published: Wiley 2005
• Subjects: Biochemistry; Organic Chemistry; Antarc*; Antarctica
• Online Access: http://dx.doi.org/10.1002/0471142700.nc0211s21; https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2F0471142700.nc0211s21; https://onlinelibrary.wiley.com/doi/pdf/10.1002/0471142700.nc0211s21; https://onlinelibrary.wiley.com/doi/full-xml/10.1002/0471142700.nc0211s21; https://currentprotocols.onlinelibrary.wiley.com/doi/pdf/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.