Neighboring Group Participation of Benzoyl Protecting Groups in C3- and C6-Fluorinated Glucose.

ABSTRACT: Fluorination is a potent method to modulate chemical properties of glycans. Here, we study how C3- and C6-fluorination of glucosyl building blocks influence the structure of the intermediate of the glycosylation reaction, the glycosyl cation. Using a combination of gas-phase infrared spectroscopy and first-principles theory, glycosyl cations generated from fluorinated and non-fluorinated monosaccharides are structurally characterized. The results indicate that neighboring group participation of the C2-benzoyl protecting group is the dominant structural motif for all building blocks, correlating with the β-selectivity observed in glycosylation reactions. The infrared signatures indicate that participation of the benzoyl group in enhanced by resonance effects. Participation of remote acyl gr

SUBMITTER: Greis K 

PROVIDER: S-EPMC9321577 | biostudies-literature | 2022 Apr

REPOSITORIES: biostudies-literature