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Efficient Synthesis of β-D-Mannosides and β-D-Talosides by Double Parallel or Double Serial Inversion
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.
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
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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.

Place, publisher, year, edition, pages
2007. Vol. 72, no 10, 3694-3701 p.
Keyword [en]
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: urn:nbn:se:kth:diva-9886DOI: 10.1021/jo062643oISI: 000246206700013Scopus ID: 2-s2.0-34248573311OAI: oai:DiVA.org:kth-9886DiVA: diva2:139846
Note

QC 20100709

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

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