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The Case for Configurational Stability of H-Phosphonate Diesters in the Presence of Diazabicyclo[5.4.0]undec-7-ene (DBU)
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2001 (English)In: Bioorganic & Medicinal Chemistry, ISSN 0968-0896, Vol. 9, no 9, 2315-2322 p.Article in journal (Refereed) Published
Abstract [en]

Configurational stability of dinucleoside H-phosphonates and the stereochemical course of their sulfurisation in the presence of diazabicyclo[5.4.0]undec-7-ene (DBU) were investigated using 31P NMR spectroscopy. It was found that under the reaction conditions and irrespective of the type of protecting groups present in the nucleoside moieties, the H-phosphonate diesters investigated did not undergo any detectable epimerisation at the phosphorus centre, and their sulfurisation with elemental sulfur in the presence of DBU, proceeded stereospecifically. Thus, we could not confirm reports from another laboratory on a stereoselective course of sulfurisation of H-phosphonate diesters and the corresponding acylphosphonates in the presence of DBU.

Place, publisher, year, edition, pages
Elsevier , 2001. Vol. 9, no 9, 2315-2322 p.
National Category
Organic Chemistry
Research subject
Organic Chemistry
URN: urn:nbn:se:su:diva-23234DOI: 10.1016/S0968-0896(01)00140-7OAI: diva2:190869
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.
Organisk kemi
National Category
Organic Chemistry
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
Available from: 2004-08-19 Created: 2004-08-19Bibliographically approved

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Stawinski, Jacek
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Department of Organic Chemistry
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