Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Chemical and Stereochemical Aspects of Oxidative Coupling of H Phosphonantes and H-Phosphonothioate Diesters: Reactions with N,N-, N,O- and O,O-Binucleophiles
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Institute of Bioorganic Chemistry, Polish Academy of Science.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
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. Vol. 2, no 2, 188-197 p.
Keyword [en]
H-phosphonates; H-phosphonothioates; binucleophiles; oxidative coupling
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-23244DOI: 10.2174/1570178053202937OAI: oai:DiVA.org:su-23244DiVA: diva2:190890
Note
Part of urn:nbn:se:su:diva-203Available from: 2004-08-19 Created: 2004-08-19 Last updated: 2010-01-11Bibliographically approved
In thesis
1. Studies on Oxidative Couplings in H-Phosphonate Chemistry
Open this publication in new window or tab >>Studies on Oxidative Couplings in H-Phosphonate 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
oxidative coupling, H-phosphonate, H-phosphonothioate, organisk kemi
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-203 (URN)91-7265-934-3 (ISBN)
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

Open Access in DiVA

No full text

Other links

Publisher's full texthttp://search.ebscohost.com/login.aspx?direct=true&db=aph&AN=16318337&site=ehost-live

Search in DiVA

By author/editor
Stawinski, Jacek
By organisation
Department of Organic Chemistry
Organic Chemistry

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 73 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf