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Synthesis of Positional Thiol Analogs of β-D-Galactopyranose
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
2007 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, Vol. 29, 4927-4934 p.Article in journal (Refereed) Published
Abstract [en]

Approaches toward the synthesis of thio- beta -D -galactose derivatives are described. These compounds were prepared from the parent carbohydrates: D-galactose, methyl P-D-galactoside and methyl P-D-glucoside, respectively. It was found that not only the strategies of protecting group introduction and selective deprotection, but also the choices of solvent and nucleophilic reagent concentration were crucial to allow the efficient introduction of sulfur at different positions of the galactose ring. The effects from the solvent, the nucleophilic reagent concentration, and the protecting group patterns have been investigated. The results clearly show that ester protecting groups play highly important roles for the synthesis of thio-containing carbohydrates, requiring nonpolar solvents to suppress the neighboring group participation. For the Lattrell-Dax (nitrite -mediated) inversion reaction, employed in the synthetic route to the 2-thio-beta-D-galactoside, intramolecular nucleophilic attack, as well as stronger stereospecific ester activation, are necessary to overcome hindrance from 4,6-O-benzylidene protection.

Place, publisher, year, edition, pages
2007. Vol. 29, 4927-4934 p.
Keyword [en]
thiosaccharides, galactose, lattrell-dax, inversion
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-9887DOI: 10.1002/ejoc.200700364ISI: 000250367600015Scopus ID: 2-s2.0-35349025393OAI: oai:DiVA.org:kth-9887DiVA: diva2:139847
Note
QC 20100709. Tidigare titel: Synthesis of Thiogalactose derivatives for S-linked OligosaccharidesAvailable from: 2009-01-27 Created: 2009-01-27 Last updated: 2017-12-14Bibliographically approved
In thesis
1. Efficient Carbohydrate Synthesis By Intra- and Supramolecular Control
Open this publication in new window or tab >>Efficient Carbohydrate Synthesis By Intra- and Supramolecular Control
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The Lattrell-Dax method of nitrite-mediated substitution of carbohydrate triflates is an efficient method to generate structures of inverse configuration. In this study, the effects of the neighboring group on the Lattrell-Dax inversion were explored. A new carbohydrate/anion host-guest system was discovered and the ambident reactivity of the nitrite anion was found to cause a complicated behavior of the reaction. It has been demonstrated that a neighboring equatorial ester group plays a highly important role in this carbohydrate epimerization reaction, restricting the nitrite N-attack, thus resulting in O-attack only and inducing the formation of inversion compounds in good yields. Based on this effect, efficient synthetic routes to a range of carbohydrate structures, notably β-D-mannosides and β-D-talosides, were designed by use of double parallel and double serial inversion. A supramolecularly activated, triggered cascade reaction was also developed. This cascade reaction is triggered by a deprotonation process that is activated by anions. It was found that the anions can activate this reaction following their hydrogen bonding tendencies to the hydroxyl group in aprotic solvents.

Place, publisher, year, edition, pages
Stockholm: KTH, 2009. 59 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2009:2
Keyword
Carbohydrate Chemistry, Supramolecular Control, Ambident Reactivity
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-9882 (URN)978-91-7415-207-4 (ISBN)
Public defence
2009-02-05, F3, KTH, Lindstedtsvägen 26, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20100709Available from: 2009-01-27 Created: 2009-01-26 Last updated: 2012-02-23Bibliographically approved
2. Dynamic Sulfur Chemistry: Screening, Evaluation and Catalysis
Open this publication in new window or tab >>Dynamic Sulfur Chemistry: Screening, Evaluation and Catalysis
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis deals with the design, formation and evaluation of dynamic systems constructed by means of sulfur-containing reversible reactions, in organic and aqueous media and under mild conditions.

In a first part, the synthesis of thioglycoside derivatives, constituting the biologically relevant starting components of the dynamic systems, is described. In addition, the pD-profile of the mutarotation process in aqueous media for a series of 1-thioaldoses is reported and revealed an astonishing beta-anomeric preference for all the carbohydrate analogs under acidic or neutral conditions.

In a second part, the phosphine-catalyzed or -mediated disulfide metathesis for dynamic system generation in organic or aqueous media is presented, respectively. The direct in situ 1H STD-NMR resolution of a dynamic carbohydrate system in the presence of a target protein (Concanavalin A) proved the suitability and compatibility of such disulfide metathesis protocols for the discovery of biologically relevant ligands.

In a third part, hemithioacetal formation is demonstrated as a new and efficient reversible reaction for the spontaneous generation of a dynamic system, despite a virtual character of the component associations in basic aqueous media. The direct in situ 1H STD-NMR identification of the best dynamic beta-galactosidase inhibitors from the dynamic HTA system was performed and the results were confirmed by inhibition studies. Thus, the HTA product formed from the reaction between 1-thiogalactopyranose and a pyridine carboxaldehyde derivative provided the best dynamic inhibitor.

In a fourth and final part, a dynamic drug design strategy, where the best inhibitors from the aforementioned dynamic HTA system were used as model for the design of non-dynamic (or “static”) beta-galactosidase inhibitors, is depicted. Inhibition studies disclosed potent leads among the set of ligands.

Place, publisher, year, edition, pages
Stockholm: KTH, 2010. 84 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2010:14
Keyword
Dynamic combinatorial chemistry; dynamic sulfur chemistry; thioglycoside; mutarotation; disulfide metathesis; hemithioacetal formation; 1H STD-NMR; inhibition; phosphine; Concanavalin A; beta-galactosidase; dynamic drug discovery.
National Category
Chemical Sciences Organic Chemistry Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-12414 (URN)978-91-7415-618-8 (ISBN)
Public defence
2010-05-12, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20100621Available from: 2010-04-22 Created: 2010-04-20 Last updated: 2010-11-29Bibliographically approved
3. Carbohydrate Synthesis and Study of Carbohydrate-Lectin Interactions Using QCM Biosensors and Microarray Technologies
Open this publication in new window or tab >>Carbohydrate Synthesis and Study of Carbohydrate-Lectin Interactions Using QCM Biosensors and Microarray Technologies
2006 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

Interactions between carbohydrates and proteins are increasingly being recognized as crucial in many biological processes, such as cellular adhesion and communication. In order to investigate the interactions of carbohydrates and proteins, the development of efficient analytic technologies, as well as novel strategies for the synthesis of carbohydrates, have to be explored. To date, several methods have been exploited to analyze interactions of carbohydrates and proteins, for example, biosensors, nuclear magnetic resonance (NMR); enzyme-linked immunosorbent assays (ELISA), X-ray crystallography and array technologies. This thesis describes the development of novel strategies for the synthesis of carbohydrates, as well as new efficient strategies to Quartz Crystal Microbalance- (QCM-) biosensors and carbohydrate microarrays technologies. These methodologies have been used to probe carbohydrate-lectin-interactions for a range of plant and animal lectins.

Place, publisher, year, edition, pages
Stockholm: KTH, 2006. 106 p.
Series
Trita-IOK, ISSN 1100-7974 ; 2006:106
Keyword
Lectins; Carbohydrates; Molecular recognition; Biosensors; Quartz crystal microbalance; Carbohydrate microarrays.
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-4177 (URN)91-7178-503-5 (ISBN)
Public defence
2006-12-01, D3, Lindstedtsvägen 5, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20100915Available from: 2006-11-22 Created: 2006-11-22 Last updated: 2011-09-05Bibliographically approved

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