Unraveling the Promoter Effect and the Roles of Counterion Exchange in Glycosylation Reaction

Overview

Journal Sci Adv

Specialties Biology
Science

Date 2023 Oct 18

PMID 37851803

Authors

Chun-Wei Chang

Mei-Huei Lin

Tsun-Yi Chiang

Chia-Hui Wu

Tzu-Chun Lin

Cheng-Chung Wang

Affiliations

Soon will be listed here.

Abstract

The stereoselectivity of glycosidic bond formation continues to pose a noteworthy hurdle in synthesizing carbohydrates, primarily due to the simultaneous occurrence of S1 and S2 processes during the glycosylation reaction. Here, we applied an in-depth analysis of the glycosylation mechanism by using low-temperature nuclear magnetic resonance and statistical approaches. A pathway driven by counterion exchanges and reaction byproducts was first discovered to outline the stereocontributions of intermediates. Moreover, the relative reactivity values, acceptor nucleophilic constants, and Hammett substituent constants (σ values) provided a general index to indicate the mechanistic pathways. These results could allow building block tailoring and reaction condition optimization in carbohydrate synthesis to be greatly facilitated and simplified.

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