A Glycosylation Mechanism Case Study: Unraveling the Mechanism of Stereospecific Self-promoted N -Glycosylations
Year: 2024
Type: preprint
Abstract: In this study, the mechanism of self-promoted N-glycosylations is extensively investigated through kinetic experiments, computational studies, and nucleophilic competition experiments. Based on the findings, the mechanism is proposed to be initiated by proton transfer from the acidic sulfonyl carbamate to the trichloroacetimidate, upon formation of an associated contact ion pair. This ion pair then collapses in an SN 1-like fashion, forming an oxocarbeniumion-like intermediate. According to the proposed mechanism, stereospecificity arises from the associated nature of all intermediates formed throughout the reaction. During the mechanistic study, it was also found that the sulfonyl carbamates have catalytic properties if a competing nucleophile is present.
Source: ChemRxiv
Institution: University of Copenhagen
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Funders: Novo Nordisk, Novo Nordisk Fonden
Award: G1413121853
OpenAlex ID: W4403687199