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Establishment of Guidelines for the Control of Glycosylation Reactions and Intermediates by Quantitative Assessment of Reactivity
Author(s) -
Chang ChunWei,
Wu ChiaHui,
Lin MeiHuei,
Liao PinHsuan,
Chang ChunChi,
Chuang HsiaoHan,
Lin SuChing,
Lam Sarah,
Verma Ved Prakash,
Hsu ChaoPing,
Wang ChengChung
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201906297
Subject(s) - glycosyl , glycosylation , reactivity (psychology) , chemistry , combinatorial chemistry , halide , glycoside , organic chemistry , biochemistry , medicine , alternative medicine , pathology
Stereocontrolled chemical glycosylation remains a major challenge despite vast efforts reported over many decades and so far still mainly relies on trial and error. Now it is shown that the relative reactivity value (RRV) of thioglycosides is an indicator for revealing stereoselectivities according to four types of acceptors. Mechanistic studies show that the reaction is dominated by two distinct intermediates: glycosyl triflates and glycosyl halides from N ‐halosuccinimide (NXS)/TfOH. The formation of glycosyl halide is highly correlated with the production of α‐glycoside. These findings enable glycosylation reactions to be foreseen by using RRVs as an α/β‐selectivity indicator and guidelines and rules to be developed for stereocontrolled glycosylation.