Self-promoted glycosylations with trichloroacetimidate glycosyl donors are demonstrated on solid-phase-anchored peptides orthogonally deprotected and tosylcarbamoylated on the side-chains of cysteine and serine, respectively. The donor scope included glucosyl as well as mannosyl trichloroacetimidates, carrying benzyl, acetyl, or isopropylidene protecting groups. Isopropylidene groups were found to be removed under the acidic conditions used for release of the neoglycopeptides from the solid support, yielding neoglycopeptides with unprotected hydroxyl groups. Glycosylation of a peptide containing a carbamoylated tyrosine was attempted as well, but the desired neoglycopeptide could not be synthesized due to thermal instability of the carbamate.
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Unraveling the Mechanism of Stereospecific Self-Promoted N-Glycosylations.
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Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen, Denmark.
Article Synopsis
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Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen Ø, Denmark.
Self-promoted glycosylations with trichloroacetimidate glycosyl donors are demonstrated on solid-phase-anchored peptides orthogonally deprotected and tosylcarbamoylated on the side-chains of cysteine and serine, respectively. The donor scope included glucosyl as well as mannosyl trichloroacetimidates, carrying benzyl, acetyl, or isopropylidene protecting groups. Isopropylidene groups were found to be removed under the acidic conditions used for release of the neoglycopeptides from the solid support, yielding neoglycopeptides with unprotected hydroxyl groups.
View Article and Find Full Text PDFSelf-Promoted Stereoselective Glycosylations - Past, Present, Future.
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Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100, Copenhagen O, Denmark.
Self-promoted glycosylations have generally not received much attention, despite having the advantages of being easy to perform and often highly stereoselective. This account covers the work done in this field and the mechanistic aspects of self-promoted glycosylations are discussed, with a main focus on the stereoselectivity of the reactions. Most self-promoted glycosylations utilize trichloroacetimidate donors, but examples of self-promoted reactions with other donors have been described and will be discussed.
View Article and Find Full Text PDFSelf-promoted and stereospecific formation of -glycosides.
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Department of Chemistry , University of Copenhagen , Universitetsparken 5, 2100 Copenhagen O , Denmark . Email:
A stereoselective and self-promoted glycosylation for the synthesis of various -glycosides and glycosyl sulfonamides from trichloroacetimidates is presented. No additional catalysts or promoters are needed in what is essentially a two-component reaction. When α-glucosyl trichloroacetimidates are employed, the reaction resulted in the stereospecific formation of the corresponding β--glucosides in high yields at ambient conditions.
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