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Stereospecific Ester Activation in Nitrite-Mediated Carbohydrate Epimerization
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
2006 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 71, no 8, 3306-3309 p.Article in journal (Refereed) Published
Abstract [en]

The Lattrell-Dax method of nitrite-mediated substitution of carbohydrate triflates is an efficient method to generate structures of inverse configuration. In the present study, epimerization of gluco- and galactopyranoside derivatives to the corresponding allo- and gulopyranoside structures by triflation/nitrite treatment has been investigated. It was found that a neighboring ester group was essential for the reactivity of the nitrite-mediated triflate, inversion. Furthermore, a good inversion yield also depended on the relative configuration of the neighboring ester group to the triflate. Only with the ester group in the equatorial position, whatever the configuration of the triflate, did the reaction proceed smoothly, whereas a neighboring axial ester group proved largely inefficient. The results were subsequently used to predict the inversion of glucopyranoside derivatives to the mannopyranoside epimers.

Place, publisher, year, edition, pages
2006. Vol. 71, no 8, 3306-3309 p.
Keyword [en]
stereoselective-synthesis, glycosides, benzoate, anions, sugars
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-9883DOI: 10.1021/jo052662iISI: 000236678100053Scopus ID: 2-s2.0-33645773127OAI: oai:DiVA.org:kth-9883DiVA: diva2:139843
Note
QC 20100709Available 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. Efficient carbohydrate synthesis by controlled inversion strategies
Open this publication in new window or tab >>Efficient carbohydrate synthesis by controlled inversion strategies
2006 (English)Licentiate thesis, comprehensive summary (Other scientific)
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 it has been demonstrated that a neighboring equatorial ester group plays a highly important role in this carbohydrate epimerization reaction, 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 the ester activation effect for neighboring groups, a double parallel as well as a double serial inversion strategy was developed.

Place, publisher, year, edition, pages
Stockholm: KTH, 2006. 40 p.
Series
Trita-IOK, ISSN 1100-7974 ; 107
Keyword
Carbohydrate Chemistry, Carbohydrate Protection, Epimerization, Inversion, Dynamic, Regioselective Control, Neighboring Group Participation
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-4179 (URN)91-7178-502-7 (ISBN)
Presentation
2006-11-30, E2, KTH, Lindstedtsvägen 3, Stockholm, 10:00
Supervisors
Note
QC 20101111Available from: 2006-11-22 Created: 2006-11-22 Last updated: 2010-11-11Bibliographically 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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