Unknown

Dataset Information

0

Matching Glycosyl Donor Reactivity to Sulfonate Leaving Group Ability Permits SN2 Glycosylations.


ABSTRACT: Here we demonstrate that highly β-selective glycosylation reactions can be achieved when the electronics of a sulfonyl chloride activator and the reactivity of a glycosyl donor hemiacetal are matched. While these reactions are compatible with the acid- and base-sensitive protecting groups that are commonly used in oligosaccharide synthesis, these protecting groups are not relied upon to control selectivity. Instead, β-selectivity arises from the stereoinversion of an α-glycosyl arylsulfonate in an SN2-like mechanism. Our mechanistic proposal is supported by NMR studies, kinetic isotope effect (KIE) measurements, and DFT calculations.

SUBMITTER: Zhuo MH 

PROVIDER: S-EPMC6814073 | biostudies-literature |

REPOSITORIES: biostudies-literature

Similar Datasets

| S-EPMC3569868 | biostudies-literature
| S-EPMC8173606 | biostudies-literature
| S-EPMC7540451 | biostudies-literature
| S-EPMC2754202 | biostudies-literature
| S-EPMC3150464 | biostudies-literature
| S-EPMC6032835 | biostudies-literature
| S-EPMC3917720 | biostudies-literature
| S-EPMC6324912 | biostudies-literature
| S-EPMC8177410 | biostudies-literature
| S-EPMC5705186 | biostudies-literature