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Mapping the Relationship between Glycosyl Acceptor Reactivity and Glycosylation Stereoselectivity
Author(s) -
van der Vorm Stefan,
van Hengst Jacob M. A.,
Bakker Marloes,
Overkleeft Herman S.,
van der Marel Gijsbert A.,
Codée Jeroen D. C.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201802899
Subject(s) - stereoselectivity , reactivity (psychology) , glycosyl , chemistry , glycosylation , acceptor , nucleophile , glycosyl donor , stereochemistry , organic chemistry , catalysis , biochemistry , medicine , physics , alternative medicine , pathology , condensed matter physics
The reactivity of both coupling partners—the glycosyl donor and acceptor—is decisive for the outcome of a glycosylation reaction, in terms of both yield and stereoselectivity. Where the reactivity of glycosyl donors is well understood and can be controlled through manipulation of the functional/protecting‐group pattern, the reactivity of glycosyl acceptor alcohols is poorly understood. We here present an operationally simple system to gauge glycosyl acceptor reactivity, which employs two conformationally locked donors with stereoselectivity that critically depends on the reactivity of the nucleophile. A wide array of acceptors was screened and their structure–reactivity/stereoselectivity relationships established. By systematically varying the protecting groups, the reactivity of glycosyl acceptors can be adjusted to attain stereoselective cis ‐glucosylations.