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Nucleoside H-phosphonates.: Part 19. Efficient entry to novel nucleotide analogues with 2-pyridyl and 4-pyridylphosphonothioate internucleotide linkages
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2004 (English)In: Tetrahedron, ISSN 0040-4020, Vol. 60, no 2, 389-395 p.Article in journal (Refereed) Published
Abstract [en]

Synthetic and 31P NMR spectroscopy studies resulted in the development of efficient protocols for the stereospecific synthesis of a novel type of nucleotide analogues, 2-pyridyl- and 4-pyridylphosphonothioates. The underlying chemistry involves formation of the P–C bond via a base-promoted reaction of suitably protected dithymidine H-phosphonothioates with N-methoxypyridinium tosylate in acetonitrile, or with trityl chloride in pyridine, to produce high yields of nucleotide analogues with a 2-pyridyl- or 4-pyridyl moiety directly bound to the phosphorus centre.

Place, publisher, year, edition, pages
Elsevier , 2004. Vol. 60, no 2, 389-395 p.
National Category
Inorganic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-23236DOI: .1016/j.tet.2003.11.010OAI: oai:DiVA.org:su-23236DiVA: diva2:190871
Note
Part of urn:nbn:se:su:diva-202Available from: 2004-08-19 Created: 2004-08-19 Last updated: 2010-01-05Bibliographically approved
In thesis
1. Studies on Transformations of H-Phosphonates into DNA Analogues Containing P-S or P-C Bonds
Open this publication in new window or tab >>Studies on Transformations of H-Phosphonates into DNA Analogues Containing P-S or P-C Bonds
2004 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In this thesis, mechanistic and synthetic studies on transformations of H-phosphonates into DNA analogues containing P-S or P-C bonds are described.

Configurational stability of dinucleoside H-phosphonates and the stereochemical course of their sulfurisation in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) were investigated. In light of these studies, the reported stereoselective sulfurisation of dinucleoside H-phosphonates and benzoylphosphonates in the presence of DBU was proved to be incorrect.

Efficient protocols for the synthesis of new nucleotide analogues with non-ionic C-phosphonate internucleotide linkages were developed. The synthesis of dinucleoside 2-pyridylphosphonates was successfully performed by a DBU-promoted reaction of H-phosphonate diesters with N-methoxypyridinium salts. The thio analogues, 2-pyridyl- and 4-pyridyl phosphonothioate diesters, could be obtained by modifying the reactions developed for their oxo counterparts. Dinucleoside 3-pyridylphosphonates were prepared via a palladium(0)-catalysed cross coupling strategy that could be extended also to the synthesis of nucleotide analogues with metal-complexing properties, i.e. terpyridyl- and bipyridylphosphonate derivatives.

Oligonucleotides modified with pyridylphosphonate internucleotide linkages have been prepared and preliminary studies on their hybridisation properties and resistance towards enzymatic degradation were performed.

Finally, nucleotidic units for the incorporation of pyridylphosphonate groups at the 5’-terminus of oligonucleotides were designed. Condensations of such units with a suitably protected nucleoside afforded after oxidation the expected dinucleoside (3’-5’)-phosphates with pyridylphosphonate monoester functions at the 5’-ends.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi, 2004. 61 p.
Keyword
Organisk kemi
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-202 (URN)91-7265-935-1 (ISBN)
Public defence
2004-09-09, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 14:00
Opponent
Supervisors
Available from: 2004-08-19 Created: 2004-08-19Bibliographically approved

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