Abstract
Phosphorylation of the easily accessible 3',5'-diesters 1a-d with diphenyl phosphorochloridate, followed by selective 5'-deacylation, affords the phosphotriester derivatives 2a-d in good yields. Alkaline treatment of 2a-d results in the formation of the 2',3'-cyclic phosphates (3a-d). The usefulness of the phosphotriester derivatives 2a-d is also demonstrated in the synthesis of the nucleotidyl-(3'-5')nucleoside 3'-phosphates U-Up (10a), U-Ap (11a), U-Cp (12a) and A-Gp (13a). The fully protected dinucleoside diphosphates 5c-8c, prepared by the phosphotriester method, are deprotected in two ways: (a) by a purely chemical method, affording the dinucleoside diphosphates in a circa one to one mixture of 2'- and 3'- isomers, 10b-13b and 10a-13a, respectively, and (b) by a mixed chemical-enzymatical approach which gives the pure 3'-phosphates (10a-13a).
Full text
PDF
Selected References
These references are in PubMed. This may not be the complete list of references from this article.
- Golankiewicz K., Jankowski A. The effective synthesis of uridylyl/3'-5'/5-methylcytidylyl/3'-5'/guanosine. Nucleic Acids Res. 1976 Mar;3(3):709–720. doi: 10.1093/nar/3.3.709. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Lohrmann R., Söll D., Hayatsu H., Ohtsuka E., Khorana H. G. Studies on polynucleotides. LI. Syntheses of the 64 possible ribotrinucleotides derived from the four major ribomononucleotides. J Am Chem Soc. 1966 Feb 20;88(4):819–829. doi: 10.1021/ja00956a039. [DOI] [PubMed] [Google Scholar]
- Markiewicz W. T., Wiewiórowski M. The modified nucleosides of tRNAs. II. Synthesis of 2'-O-methylcytidylyl (3'-5') cytidine. Nucleic Acids Res. 1975 Jun;2(6):951–960. doi: 10.1093/nar/2.6.951. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Reese C. B., Stewart J. C., van Boom J. H., de Leeuw H. P., Nagel J., de Rooy J. F. The synthesis of oligoribonucleotides. Part XI. Preparation of ribonucleoside 2'-acetal 3'-esters by selective deacylation. J Chem Soc Perkin 1. 1975;(10):934–942. doi: 10.1039/p19750000934. [DOI] [PubMed] [Google Scholar]
- Rhaese H. J., Siehr W., Cramer F. Synthese von Dinucleotiden der Ribose-Reihe mit terminaler 3'-Phosphat-Gruppe. Justus Liebigs Ann Chem. 1967 Apr;703:215–224. doi: 10.1002/jlac.19677030125. [DOI] [PubMed] [Google Scholar]
- SOELL D., KHORANA H. G. STUDIES ON POLYNUCLEOTIDES. XXXV. THE SPECIFIC SYNTHESIS OF C3'-C5'-LINKED RIBOOLIGONUCLEOTIDES. 8. THE SYNTHESIS OF RIBODINUCLEOTIDES BEARING 3'-PHOSPHOMONOESTER GROUPS. J Am Chem Soc. 1965 Jan 20;87:350–359. doi: 10.1021/ja01080a036. [DOI] [PubMed] [Google Scholar]
- van Boom J. H., de Rooy J. F., Reese C. B. The synthesis of oligoribonucleotides. X. Preparation of 2',3'-cyclic phosphates of ribonucleosides and diribonucleoside phosphates via phosphotriester intermediates. J Chem Soc Perkin 1. 1973;21:2513–2517. doi: 10.1039/p19730002513. [DOI] [PubMed] [Google Scholar]