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. Self-promoted glycosylation strategies can provide a basis for new stereoselective glycosylation methodologies.
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Unraveling the Mechanism of Stereospecific Self-Promoted N-Glycosylations.
Chemistry
November 2024
Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen, Denmark.
Article Synopsis
- The study investigates how self-promoted N-glycosylations work through experiments that test reaction rates, computer simulations, and competing reactions with different nucleophiles.
- It proposes that the reaction starts with a proton transfer from a sulfonyl carbamate to a trichloroacetimidate, forming an ion pair that leads to a specific intermediate structure.
- The findings suggest that the reaction produces specific stereoisomers because of the nature of the intermediates, and the sulfonyl carbamates can act as catalysts when competing nucleophiles are present.
Self-Promoted Glycosylation of Carbamoylated Peptides on Solid Phase.
Chempluschem
August 2024
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.
Chem Rec
November 2021
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.
Chem Sci
May 2019
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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