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Studies on Oxidative Couplings in H-Phosphonate Chemistry
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2004 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In this thesis oxidative coupling of H-phosphonate and H phosphonothioate diesters with different alcohols and amines are presented. Since the reactions with alcohols previously have been particularly unfavourable due to competing side reactions, a modified protocol leading to high coupling yields of structurally diverse hydroxylic components was developed. The phosphorylation reaction was studied using 31P NMR spectroscopy and for the first time the previously only postulated reactive intermediate involved in these reactions was observed.

The use of iodine in combination with a bulky chlorosilane in pyridine was found to have a profound effect on both the suppression of side reactions and the rate of the oxidative couplings, and led to a clean formation of phosphorylated products in high yields. This synthetic protocol was then extended to include coupling reactions with bis-functional reagents containing hexamethylene linkers to provide handles for derivatisations of oligonucleotides.

A synthetic protocol consisting of the stereospecific oxidative coupling of amines with H-phosphonate diesters to produce phosphoroamidates was designed in such a way that it permitted control of the stereochemical outcome of the reactions.

Based on a silylation-mediated reaction utilising phenyl H phosphonothioate monoester as a thiophosphonyl transferring agent, a method was developed and used for the preparation of H-phosphonothioate building blocks for the synthesis of DNA analogues.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi , 2004. , 42 p.
Keyword [en]
oxidative coupling, H-phosphonate, H-phosphonothioate
Keyword [sv]
organisk kemi
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-203ISBN: 91-7265-934-3 (print)OAI: oai:DiVA.org:su-203DiVA: diva2:190892
Public defence
2004-09-10, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 14:00
Opponent
Supervisors
Available from: 2004-08-19 Created: 2004-08-19Bibliographically approved
List of papers
1. Reinvestigation of the 31P NMR Evidence for the Formation of Diorganyl Phosphoropyridinium Intermediates
Open this publication in new window or tab >>Reinvestigation of the 31P NMR Evidence for the Formation of Diorganyl Phosphoropyridinium Intermediates
2001 (English)In: Journal of the Chemical Society Perkin Transactions 2, ISSN 1364-5471, no 12, 2263-2266 p.Article in journal (Refereed) Published
Place, publisher, year, edition, pages
london: Royal Society of Chemistry, 2001
Identifiers
urn:nbn:se:su:diva-23241 (URN)
Note
Part of urn:nbn:se:su:diva-203Available from: 2004-08-19 Created: 2004-08-19 Last updated: 2010-01-29Bibliographically approved
2. Oxidative Coupling of H-Phosphonate and H-Phosphonothioate Diesters: Iodine as a Reagent and a Catalyst
Open this publication in new window or tab >>Oxidative Coupling of H-Phosphonate and H-Phosphonothioate Diesters: Iodine as a Reagent and a Catalyst
2002 (English)In: Collection Symposium Series, Vol. 5, 87-92 p.Article in journal (Refereed) Published
Place, publisher, year, edition, pages
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic,, 2002
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-23242 (URN)
Note
Part of urn:nbn:se:su:diva-203Available from: 2004-08-19 Created: 2004-08-19 Last updated: 2010-01-05Bibliographically approved
3. Controlling Stereochemistry During Oxidative Coupling: Preparation of Rp or Sp Phosphoramidates from One P-Chiral Precursor
Open this publication in new window or tab >>Controlling Stereochemistry During Oxidative Coupling: Preparation of Rp or Sp Phosphoramidates from One P-Chiral Precursor
2004 (English)In: Chemical Communications, ISSN 1359-7345, Vol. 22, 2566-2567 p.Article in journal (Refereed) Published
Abstract [en]

Stereochemical outcome of oxidative coupling of H-phosphonate diesters with amines, promoted by iodine, can be controlled to obtain the corresponding phosphoramidate diesters with inversion or with retention of configuration at the phosphorus centre

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2004
Keyword
H-PHOSPHONOTHIOATE DIESTERS; PHOSPHONATE; DERIVATIVES; PHOSPHOLIPIDS; ANALOGS; ESTERS
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-23243 (URN)10.1039/b411451e (DOI)
Note
Part of urn:nbn:se:su:diva-203Available from: 2004-08-19 Created: 2004-08-19 Last updated: 2010-01-05Bibliographically approved
4. Chemical and Stereochemical Aspects of Oxidative Coupling of H Phosphonantes and H-Phosphonothioate Diesters: Reactions with N,N-, N,O- and O,O-Binucleophiles
Open this publication in new window or tab >>Chemical and Stereochemical Aspects of Oxidative Coupling of H Phosphonantes and H-Phosphonothioate Diesters: Reactions with N,N-, N,O- and O,O-Binucleophiles
2005 (English)In: Letters in organic chemistry, ISSN 1570-1786, Vol. 2, no 2, 188-197 p.Article in journal (Refereed) Published
Abstract [en]

Efficient protocols for oxidative coupling of dinucleoside H-phosphonate and dinucleoside Hphosphonothioate diesters with 6-aminohexan-1-ol, hexane-1,6-diamine, and hexane-1,6-diol, promoted by iodine were developed. In the instance of coupling with O-nucleophiles, the presence of t-butyldiphenylsilyl chloride and excess of iodine during oxidative coupling were found to have beneficial effect for these reactions in terms of rates and purity of the formed products

Place, publisher, year, edition, pages
Bentham Science Publ. Ltd., 2005
Keyword
H-phosphonates; H-phosphonothioates; binucleophiles; oxidative coupling
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-23244 (URN)10.2174/1570178053202937 (DOI)
Note
Part of urn:nbn:se:su:diva-203Available from: 2004-08-19 Created: 2004-08-19 Last updated: 2010-01-11Bibliographically approved
5. Silylation-Mediated Transesterification of Phenyl H-Phosphonothioate: A New Entry to Nucleoside H-Phosphonothioate Monoesters
Open this publication in new window or tab >>Silylation-Mediated Transesterification of Phenyl H-Phosphonothioate: A New Entry to Nucleoside H-Phosphonothioate Monoesters
2004 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, no 24, 5111-5114 p.Article in journal (Refereed) Published
Abstract [en]

O-Phenyl H-phosphonothioate undergoes a facile transesterification with suitably protected nucleosides upon in situ silylation with tert-butyldiphenylsilyl chloride in pyridine/toluene to produce the corresponding 3'-H-phosphonothioates in good yields. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).

Keyword
phosphonates; phosphonothioates; silylation; transesterification
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-23245 (URN)10.1002/ejoc.200400550 (DOI)
Note
Part of urn:nbn:se:su:diva-203Available from: 2004-08-19 Created: 2004-08-19 Last updated: 2017-12-13Bibliographically approved

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