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Synthesis of All Eight L ‐Glycopyranosyl Donors Using CH Activation
Author(s) -
Frihed Tobias Gylling,
Pedersen Christian Marcus,
Bols Mikael
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201408209
Subject(s) - chemistry , iridium , intramolecular force , glycosylation , catalysis , acetylation , silylation , stereochemistry , sulfide , medicinal chemistry , organic chemistry , biochemistry , gene
The synthesis of all eight rare, but biologically important L ‐hexoses as the according thioglycosyl donors was achieved through a procedure involving the CH activation of their corresponding 6‐deoxy‐ L ‐hexoses. The key steps of the procedure were the silylation of the OH group at C4 followed by an intramolecular CH activation of the methyl group in γ‐position; both steps were catalyzed by iridium. The following Fleming–Tamao oxidation and acetylation gave the suitably protected L ‐hexoses. This is the first general method for the preparation of all eight L ‐hexoses as their thioglycosyl donors ready for glycosylation and the first example of an iridium‐catalyzed C(sp 3 )H activation on sulfide‐containing compounds.