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Studies on nucleoside H-phosphonoselenoate chemistry and chalcogen exchange reaction between P(V) and P(III) compounds
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2005 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In this thesis, the chemistry of compounds containing P-Se bonds has been studied. As a new addition to this class of compounds, H-phosphonoselenoate monoesters, have been introduced and two synthetic pathways for their preparation have been developed.

The reactivity of H-phosphonoselenoate monoesters towards a variety of condensing agents has been studied. From these, efficient conditions for the synthesis of H-phosphonoselenoate diesters have been developed. The produced diesters have subsequently been used in oxidative transformations, which gave access to the corresponding P(V) compounds, e.g. dinucleoside phosphoroselenoates or dinucleoside phosphoroselenothioates.

Furthermore, a new selenizing agent, triphenyl phosphoroselenoate, has been developed for selenization of P(III) compounds. This reagent has high solubility in organic solvents and was found to convert phosphite triesters and H-phosphonate diesters efficiently into the corresponding phosphoroselenoate derivatives.

The selenization of P(III) compounds with triphenyl phosphoroselenoate proceeds through a selenium transfer reaction. A computational study was performed to gain insight into a mechanism for this reaction. The results indicate that the transfer of selenium or sulfur from P(V) to P(III) compounds proceeds most likely via an X-philic attack of the P(III) nucleophile on the chalcogen of the P(V) species. For the transfer of oxygen, the reaction may also proceed via an edge attack on the P=O bond.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi , 2005. , 38 p.
Keyword [en]
Phosphorus chemistry, H-phosphonate, H-phosphonoselenoate, nucleotide analogues, selenization, selenium transfer, phosphoroselenoate
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-736ISBN: 91-7155-163-8 (print)OAI: oai:DiVA.org:su-736DiVA: diva2:198120
Public defence
2005-12-02, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 14:00
Opponent
Supervisors
Available from: 2005-11-11 Created: 2005-11-11Bibliographically approved
List of papers
1. Nucleoside H-phosphonates. Part 19: Novel nucleotide analogues H-phosphonoselenoate mono- and diesters
Open this publication in new window or tab >>Nucleoside H-phosphonates. Part 19: Novel nucleotide analogues H-phosphonoselenoate mono- and diesters
2002 In: Tetrahedron Letters, ISSN 0040-4039, Vol. 43, no 3, 515-518 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24688 (URN)
Note
Part of urn:nbn:se:su:diva-736Available from: 2005-11-11 Created: 2005-11-11Bibliographically approved
2. Preparation of nucleoside H-phosphonoselenoate monoesters via the phosphinate approach
Open this publication in new window or tab >>Preparation of nucleoside H-phosphonoselenoate monoesters via the phosphinate approach
2005 (English)In: Nucleosides, Nucleotides & Nucleic Acids, ISSN 1525-7770, E-ISSN 1532-2335, Vol. 24, no 10-12, 1627-1633 p.Article in journal (Refereed) Published
Abstract [en]

An efficient entry to nucleoside 3'-H-phosphonoselenoate monoesters via phosphinate intermediates was developed. It involves a reaction of suitably protected nucleosides with triethylammonium phosphinate in the presence of pivaloyl chloride, followed by selenization of the intermediate nucleoside phosphinates with triphenylphosphine selenide, to produce the corresponding nucleoside H-phosphonoselenoates in 86-92% yields.

Place, publisher, year, edition, pages
Taylor & Francis, 2005
Keyword
H-Phosphonoselenoate monoesters; H-Phosphinates; H-Phosphonate approach; Triphenylphosphine selenide; Triphenyl phosphoroselenoate
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-24689 (URN)10.1080/15257770500266883 (DOI)
Note
Part of urn:nbn:se:su:diva-736Available from: 2005-11-11 Created: 2005-11-11 Last updated: 2010-12-08Bibliographically approved
3. Nucleoside H-phosphonates XX: Efficient method for the preparation of nucleoside H-phosphonoselenoate monoesters
Open this publication in new window or tab >>Nucleoside H-phosphonates XX: Efficient method for the preparation of nucleoside H-phosphonoselenoate monoesters
2005 (English)In: Synthesis (Stuttgart), ISSN 0039-7881, E-ISSN 1437-210X, no 10, 1668-1674 p.Article in journal (Refereed) Published
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-24690 (URN)10.1055/s-2005-865300 (DOI)000230380900020 ()
Note

Part of urn:nbn:se:su:diva-736

Available from: 2005-11-11 Created: 2005-11-11 Last updated: 2015-10-14Bibliographically approved
4. Synthetic and 31P NMR studies on the preparation and oxidation of dinucleoside H-phosphonoselenoates
Open this publication in new window or tab >>Synthetic and 31P NMR studies on the preparation and oxidation of dinucleoside H-phosphonoselenoates
Manuscript (Other academic)
Identifiers
urn:nbn:se:su:diva-24691 (URN)
Note
Part of urn:nbn:se:su:diva-736Available from: 2005-11-11 Created: 2005-11-11 Last updated: 2010-01-13Bibliographically approved
5. Triphenyl phosphoroselenoate - a new selenizing agent for P(III) compounds
Open this publication in new window or tab >>Triphenyl phosphoroselenoate - a new selenizing agent for P(III) compounds
2002 In: Collection Symposium Series, Vol. 5, 290-294 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24692 (URN)
Note
Part of urn:nbn:se:su:diva-736Available from: 2005-11-11 Created: 2005-11-11Bibliographically approved
6. Theoretical investigation on the mechanism of chalcogen exchange reaction between P(V) and P(III) compounds
Open this publication in new window or tab >>Theoretical investigation on the mechanism of chalcogen exchange reaction between P(V) and P(III) compounds
2005 In: Journal of Organometallic chemistry, ISSN 0022-328X, Vol. 690, 2571-2576 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-24693 (URN)
Note
Part of urn:nbn:se:su:diva-736Available from: 2005-11-11 Created: 2005-11-11Bibliographically approved

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