Premium
Reactivity–Stereoselectivity Mapping for the Assembly of Mycobacterium marinum Lipooligosaccharides
Author(s) -
Hansen Thomas,
Ofman Tim P.,
Vlaming Joey G. C.,
Gagarinov Ivan A.,
Beek Jessey,
Goté Tessa A.,
Tichem Jacoba M.,
Ruijgrok Gijs,
Overkleeft Herman S.,
Filippov Dmitri V.,
Marel Gijsbert A.,
Codée Jeroen D. C.
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202010280
Subject(s) - reactivity (psychology) , stereoselectivity , stereocenter , glycosidic bond , mycobacterium marinum , rational design , chemistry , monosaccharide , glycosylation , glycan , stereochemistry , combinatorial chemistry , biology , biochemistry , mycobacterium , genetics , bacteria , enantioselective synthesis , catalysis , medicine , glycoprotein , enzyme , alternative medicine , pathology
Abstract The assembly of complex bacterial glycans presenting rare structural motifs and cis ‐glycosidic linkages is significantly obstructed by the lack of knowledge of the reactivity of the constituting building blocks and the stereoselectivity of the reactions in which they partake. We here report a strategy to map the reactivity of carbohydrate building blocks and apply it to understand the reactivity of the bacterial sugar, caryophyllose, a rare C12‐monosaccharide, containing a characteristic tetrasubstituted stereocenter. We mapped reactivity–stereoselectivity relationships for caryophyllose donor and acceptor glycosides by a systematic series of glycosylations in combination with the detection and characterization of different reactive intermediates using experimental and computational techniques. The insights garnered from these studies enabled the rational design of building blocks with the required properties to assemble mycobacterial lipooligosaccharide fragments of M. marinum .