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Silylation-Mediated Transesterification of Phenyl H-Phosphonothioate: A New Entry to Nucleoside H-Phosphonothioate Monoesters
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
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).

Place, publisher, year, edition, pages
2004. no 24, 5111-5114 p.
Keyword [en]
phosphonates; phosphonothioates; silylation; transesterification
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-23245DOI: 10.1002/ejoc.200400550OAI: oai:DiVA.org:su-23245DiVA: diva2:190891
Note
Part of urn:nbn:se:su:diva-203Available from: 2004-08-19 Created: 2004-08-19 Last updated: 2010-04-28Bibliographically 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
2. Expanding the H-phosphonate and H-phosphonothioate chemistry towards biologically important phosphate analogs
Open this publication in new window or tab >>Expanding the H-phosphonate and H-phosphonothioate chemistry towards biologically important phosphate analogs
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis focuses on chemical transformations of H-phosphonate and H-phosphonothioate and can be divided in two parts. The first part, is devoted to the development of the palladium-catalyzed P-C bond formation. Both mechanistic and synthetic studies of the transformations have been performed. The stereochemical aspects of palladium catalyzed arylation and benzylation of DNA analogs containing H-phosphonate and H-phosphonothioate have been studied.

In chapter 5 the condensation using Mitsunobu reaction of H-phosphonate function and nucleoside has been studied. Efficient protocols for the synthesis of nucleoside H-phosphonate monoester were developed.

The last chapter deals with development of silylation-mediated transesterfication of phenyl H-phosphonothioate as a thiophosphonylating agent. The methodology was used to prepare nucleoside H-phosphonothioate monomeric building blocks in good yields.

Publisher
40 p.
Keyword
Phosphonate, phosphonothioate, H-phosphonate
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-37514 (URN)978-91-7447-020-8 (ISBN)
Public defence
2010-05-21, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Accepted. Available from: 2010-04-29 Created: 2010-03-08 Last updated: 2010-04-28Bibliographically approved

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