Intramolecular 1,8-hydrogen-atom transfer reactions in (1 -> 4)-o-disaccharide systems: conformational and stereochemical requirements

C.G. Francisco, A.J. Herrera, A.R. Kennedy, A. Martin, D. Melian, I. Perez-Martin, L.M. Quintanal, E. Suarez

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

The stereochemical and conformational factors controlling the intramolecular hydrogen-atom transfer (HAT) reaction between the two pyranose units in a (14)-O-disaccharide when promoted by a primary 6-O-yl radical are studied. Models with -D-Glcp-(14)--D-Glcp, -L-Rhamp-(14)--D-Galp or -D-Manp-(14)--L-Gulp skeletons led exclusively to the abstraction of the hydrogen from HC-5 and the formation, through a nine-membered transition state, of a 1,3,5-trioxocane ring system in a stable boat-chair conformation. Notwithstanding, derivatives of -L-Rhamp-(14)--D-Glcp or -D-Manp-(14)--D-Galp exclusively abstract the hydrogen from HC-1 through a seven-membered transition state and, therefore, lead to an interglycosidic spiro ortho ester.
LanguageEnglish
Pages10369-10381
Number of pages12
JournalChemistry - A European Journal
Volume14
Issue number33
DOIs
Publication statusPublished - 2008

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Disaccharides
Hydrogen
Atoms
Boats
Conformations
Esters
Derivatives

Keywords

  • carbohydrates
  • disaccharides
  • esters
  • radical reactions
  • trioxocane

Cite this

Francisco, C.G. ; Herrera, A.J. ; Kennedy, A.R. ; Martin, A. ; Melian, D. ; Perez-Martin, I. ; Quintanal, L.M. ; Suarez, E. / Intramolecular 1,8-hydrogen-atom transfer reactions in (1 -> 4)-o-disaccharide systems: conformational and stereochemical requirements. In: Chemistry - A European Journal. 2008 ; Vol. 14, No. 33. pp. 10369-10381.
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Intramolecular 1,8-hydrogen-atom transfer reactions in (1 -> 4)-o-disaccharide systems: conformational and stereochemical requirements. / Francisco, C.G.; Herrera, A.J.; Kennedy, A.R.; Martin, A.; Melian, D.; Perez-Martin, I.; Quintanal, L.M.; Suarez, E.

In: Chemistry - A European Journal, Vol. 14, No. 33, 2008, p. 10369-10381.

Research output: Contribution to journalArticle

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AU - Francisco, C.G.

AU - Herrera, A.J.

AU - Kennedy, A.R.

AU - Martin, A.

AU - Melian, D.

AU - Perez-Martin, I.

AU - Quintanal, L.M.

AU - Suarez, E.

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AB - The stereochemical and conformational factors controlling the intramolecular hydrogen-atom transfer (HAT) reaction between the two pyranose units in a (14)-O-disaccharide when promoted by a primary 6-O-yl radical are studied. Models with -D-Glcp-(14)--D-Glcp, -L-Rhamp-(14)--D-Galp or -D-Manp-(14)--L-Gulp skeletons led exclusively to the abstraction of the hydrogen from HC-5 and the formation, through a nine-membered transition state, of a 1,3,5-trioxocane ring system in a stable boat-chair conformation. Notwithstanding, derivatives of -L-Rhamp-(14)--D-Glcp or -D-Manp-(14)--D-Galp exclusively abstract the hydrogen from HC-1 through a seven-membered transition state and, therefore, lead to an interglycosidic spiro ortho ester.

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KW - disaccharides

KW - esters

KW - radical reactions

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