"Super armed" glycosyl donors: Conformational arming of thioglycosides by silylation

Christian Marcus Pedersen, Larsulrik R. Nordstroem, Mikael Bols

Research output: Contribution to journalArticle

118 Citations (Scopus)

Abstract

Glycosyl donors protected with bulky silyl protective groups (tert-butyldimethylsilyl, TBS), on the 2-, 3-, and 4-OH groups were found to have superior reactivity compared with benzylated thioglucosides. The enhanced reactivity is explained by the stereoelectronic effects associated with the conformational change induced by the silylation. A TBS silylated thioglucoside donor has axial OR groups, whereas a benzylated thioglucoside has equatorial OR groups, leading to much more favorable charge-dipole interactions in the transition state. This concept could be used to create "super armed" glucosyl, mannosyl, rhamnosyl, and galactosyl donors, which could cross-couple with the armed acceptors, phenyl 2,3,4-tri-O-benzyl-β-D-thioglucoside or phenyl 2,3,6-tri-O-benzyl-β-D-thioglucoside, to give the corresponding armed disaccharides in good to excellent yields.

Original languageEnglish (US)
Pages (from-to)9222-9235
Number of pages14
JournalJournal of the American Chemical Society
Volume129
Issue number29
DOIs
StatePublished - Jul 25 2007
Externally publishedYes

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Thioglucosides
Thioglycosides
Disaccharides

ASJC Scopus subject areas

  • Chemistry(all)

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"Super armed" glycosyl donors : Conformational arming of thioglycosides by silylation. / Pedersen, Christian Marcus; Nordstroem, Larsulrik R.; Bols, Mikael.

In: Journal of the American Chemical Society, Vol. 129, No. 29, 25.07.2007, p. 9222-9235.

Research output: Contribution to journalArticle

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abstract = "Glycosyl donors protected with bulky silyl protective groups (tert-butyldimethylsilyl, TBS), on the 2-, 3-, and 4-OH groups were found to have superior reactivity compared with benzylated thioglucosides. The enhanced reactivity is explained by the stereoelectronic effects associated with the conformational change induced by the silylation. A TBS silylated thioglucoside donor has axial OR groups, whereas a benzylated thioglucoside has equatorial OR groups, leading to much more favorable charge-dipole interactions in the transition state. This concept could be used to create {"}super armed{"} glucosyl, mannosyl, rhamnosyl, and galactosyl donors, which could cross-couple with the armed acceptors, phenyl 2,3,4-tri-O-benzyl-β-D-thioglucoside or phenyl 2,3,6-tri-O-benzyl-β-D-thioglucoside, to give the corresponding armed disaccharides in good to excellent yields.",
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