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Expanding the H-phosphonate and H-phosphonothioate chemistry towards biologically important phosphate analogs
Stockholm University, Faculty of Science, Department of Organic Chemistry. (Jacek Stawinski)
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.

Place, publisher, year, edition, pages
2010. , 40 p.
Keyword [en]
Phosphonate, phosphonothioate, H-phosphonate
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-37514ISBN: 978-91-7447-020-8 (print)OAI: oai:DiVA.org:su-37514DiVA: diva2:302629
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At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Accepted.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
List of papers
1. Synthetic Studies on the Preparation of Dinucleoside Phenyl-Phosphonates and Phenyl-Phosphonothioates via Palladium(0) Catalyzed Cross-Coupling
Open this publication in new window or tab >>Synthetic Studies on the Preparation of Dinucleoside Phenyl-Phosphonates and Phenyl-Phosphonothioates via Palladium(0) Catalyzed Cross-Coupling
2005 (English)In: / [ed] Michal Hocek, 2005, 195-199 p.Conference paper, Published paper (Refereed)
Abstract [en]

Separate diastereomers of protected dithymidine (3'-5')-phenylphosphonates and dithymidine (3'-5')phenylphosphonothioate were obtained via a palladium(0) catalysed stereo-specific cross-coupling reaction of separate diastereomers of corresponding dinucleoside H-phosphonate and dinucleoside H-phosphonothioate with halobenzenes.

Series
Collection Symposium Series, 7
Keyword
phenylphosphonate, phenylphosphonothioate
National Category
Other Basic Medicine
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-38772 (URN)
Conference
XIII Symposium on Chemistry of Nucleic Acid Components
Available from: 2010-04-28 Created: 2010-04-28 Last updated: 2010-04-28Bibliographically approved
2. Palladium(0)-catalyzed benzylation of H-phosphonate diesters: An efficient entry to benzylphosphonates
Open this publication in new window or tab >>Palladium(0)-catalyzed benzylation of H-phosphonate diesters: An efficient entry to benzylphosphonates
2009 (English)In: Synlett: Accounts and Rapid Communications in Synthetic Organic Chemistry, ISSN 0936-5214, E-ISSN 1437-2096, no 2, 225-228 p.Article in journal (Refereed) Published
Abstract [en]

A new, efficient method for the synthesis of benzylphosphonate diesters via a palladium(0)-catalyzed cross-coupling reaction between benzyl halides and H-phosphonate diesters, using Pd(OAc)2 as a palladium source and Xantphos as a supporting ligand, has been developed.

Keyword
benzylphosphonates, palladium cross-coupling, H-phos­phonates, C-phosphonates
National Category
Other Basic Medicine
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-26326 (URN)10.1055/s-0028-1087522 (DOI)000262988100011 ()
Available from: 2009-03-18 Created: 2009-03-18 Last updated: 2017-12-13Bibliographically approved
3. Preparation of benzylphosphonates via a palladium(0)-catalyzed cross-coupling of H-phosphonate diesters with benzyl halides. Synthetic and mechanistic studies
Open this publication in new window or tab >>Preparation of benzylphosphonates via a palladium(0)-catalyzed cross-coupling of H-phosphonate diesters with benzyl halides. Synthetic and mechanistic studies
2010 (English)In: New Journal of Chemistry, ISSN 1144-0546, E-ISSN 1369-9261, Vol. 34, no 5, 967-975 p.Article in journal (Refereed) Published
Abstract [en]

We have developed a new, efficient method for the synthesis of benzylphosphonate andbenzylphosphonothioate diesters via a palladium(0)-catalyzed cross-coupling reaction betweenbenzyl halides and H-phosphonate or H-phosphonothioate diesters, using Pd2(dba)3(CHCl3)as a palladium source and Xantphos as a supporting ligand. Some mechanistic aspects of thesereactions were investigated using 31P NMR spectroscopy.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2010
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-38775 (URN)10.1039/b9nj00585d (DOI)000277399200022 ()
Funder
Swedish Research Council
Available from: 2010-04-28 Created: 2010-04-28 Last updated: 2017-12-12Bibliographically approved
4. Synthetic studies on the preparation of nucleoside 5'-H-phosphonate monoesters under the Mitsunobu reaction conditions
Open this publication in new window or tab >>Synthetic studies on the preparation of nucleoside 5'-H-phosphonate monoesters under the Mitsunobu reaction conditions
2009 (English)In: ARKIVOC, ISSN 1424-6376, no 3, 20-27 p.Article in journal (Refereed) Published
Abstract [en]

A reaction of suitably protected nucleosides with phosphonic acid in the presence of diethyl azodicarboxylate and triphenylphosphine in pyridine provided in good yields the corresponding 5’-H-phosphonate monoesters.

Keyword
H-Phosphonate monoesters, phosphonic acid, the Mitsunobu reaction
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-30074 (URN)000265191400004 ()
Note

Dedicated to Professor Harri Lönnberg on the occasion of his 60th birthday (in part III)

Title according to journal's index: Synthetic studies on nucleoside 5'-H-phosphonate monoesters under Mitsunobu reaction conditions

Available from: 2009-10-01 Created: 2009-10-01 Last updated: 2017-12-13Bibliographically 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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