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Efficient carbohydrate synthesis by controlled inversion strategies
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
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 [en]
Carbohydrate Chemistry, Carbohydrate Protection, Epimerization, Inversion, Dynamic, Regioselective Control, Neighboring Group Participation
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-4179ISBN: 91-7178-502-7 (print)OAI: oai:DiVA.org:kth-4179DiVA: diva2:11097
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
List of papers
1. Solvent-dependent, kinetically controlled stereoselective synthesis of 3- and 4- thioglycosides
Open this publication in new window or tab >>Solvent-dependent, kinetically controlled stereoselective synthesis of 3- and 4- thioglycosides
2005 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 70, no 17, 6952-6955 p.Article in journal (Refereed) Published
Abstract [en]

Facile approaches to prepare 3- and 4-thioglycosides of the galacto, gulo, and gluco type from the parent triflates are presented. The dependencies of the solvent and the protecting group pattern, as well as the configuration of the neighboring and leaving groups, have been studied for these reactions. The results clearly show that the efficient stereo-selective synthesis of methyl 3-thin-galactoside depends highly on the solvent and the nucleophile concentration.

Keyword
Derivatives, Solvents, Stereochemistry, Synthesis (chemical)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-6395 (URN)10.1021/jo050650r (DOI)000231183000054 ()2-s2.0-23644434820 (Scopus ID)
Note
QC 20100915Available from: 2006-11-22 Created: 2006-11-22 Last updated: 2010-11-11Bibliographically approved
2. Stereospecific Ester Activation in Nitrite-Mediated Carbohydrate Epimerization
Open this publication in new window or tab >>Stereospecific Ester Activation in Nitrite-Mediated Carbohydrate Epimerization
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.

Keyword
stereoselective-synthesis, glycosides, benzoate, anions, sugars
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-9883 (URN)10.1021/jo052662i (DOI)000236678100053 ()2-s2.0-33645773127 (Scopus ID)
Note
QC 20100709Available from: 2009-01-27 Created: 2009-01-27 Last updated: 2010-09-15Bibliographically approved
3. Reagent-dependent regioselective control in multiple carbohydrate esterifications
Open this publication in new window or tab >>Reagent-dependent regioselective control in multiple carbohydrate esterifications
2007 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 72, no 4, 1499-1502 p.Article in journal (Refereed) Published
Abstract [en]

Regioselective control in organotin-mediated multiple acylation of carbohydrates is presented. The acylation reagent could be efficiently used to direct the product formation. Reagent-dependent thermodynamic and kinetic control and dynamic assistance mechanisms are suggested, resulting in the efficient preparation of building blocks that normally require many steps with traditional synthesis.

Keyword
D-GLUCOPYRANOSIDE; HYDROXYL GROUP; BENZOYLATION; OLIGOSACCHARIDES; DERIVATIVES; SELECTIVITY; ALKYLATION; ACTIVATION; ACYLATION; SUGARS
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-6397 (URN)10.1021/jo0620821 (DOI)000244071100062 ()2-s2.0-33846986010 (Scopus ID)
Note
QC 20100709Available from: 2006-11-22 Created: 2006-11-22 Last updated: 2010-12-03Bibliographically approved
4. Efficient Synthesis of β-D-Mannosides and β-D-Talosides by Double Parallel or Double Serial Inversion
Open this publication in new window or tab >>Efficient Synthesis of β-D-Mannosides and β-D-Talosides by Double Parallel or Double Serial Inversion
Show others...
2007 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 72, no 10, 3694-3701 p.Article in journal (Refereed) Published
Abstract [en]

A neighboring equatorial ester group plays a highly important role in the Lattrell-Dax (nitrite-mediated) carbohydrate epimerization reaction, inducing the formation of inversion compounds in good yields. On the basis of this effect, efficient synthetic routes to beta-D-mannosides and beta-D-talosides, from the corresponding beta-D-galactosides and beta-D-glucosides, have been designed. The present routes are based on multiple regioselective acylation via the respective stannylene intermediates, followed by inversions to the corresponding manno- and talopyranoside structures by nitrite or acetate substitution. It was found that the ester group was able to induce the inversion of its two neighboring groups in high yields following either a double parallel or a double serial inversion process. By combination of direct inversion, and neighboring- as well as remote-group participation, several beta-D-mannoside and beta-D-taloside derivatives were very conveniently obtained in good yields.

Keyword
INTRAMOLECULAR AGLYCON DELIVERY; STEREOSELECTIVE-SYNTHESIS; CORE PENTASACCHARIDE; D-MANNOPYRANOSIDES; N-GLYCANS; CHEMOENZYMATIC SYNTHESIS; LINKED GLYCOPROTEINS; PRACTICAL SYNTHESIS; CHEMICAL-SYNTHESIS; NITRITE ANIONS
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-9886 (URN)10.1021/jo062643o (DOI)000246206700013 ()2-s2.0-34248573311 (Scopus ID)
Note

QC 20100709

Available from: 2009-01-27 Created: 2009-01-27 Last updated: 2016-05-09Bibliographically approved

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