Premium
Pyranosides with 2,3‐ trans Carbamate Groups: Exocyclic or Endocyclic Cleavage Reaction?
Author(s) -
Manabe Shino,
Ito Yukishige
Publication year - 2014
Publication title -
the chemical record
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.61
H-Index - 78
eISSN - 1528-0691
pISSN - 1527-8999
DOI - 10.1002/tcr.201402004
Subject(s) - chemistry , carbamate , glycosyl , glycosylation , cleavage (geology) , intramolecular force , stereochemistry , oligosaccharide , glycosyl donor , selectivity , medicinal chemistry , organic chemistry , catalysis , biochemistry , geotechnical engineering , fracture (geology) , engineering
Pyranosides with 2,3‐ trans carbamate groups exhibit high 1,2‐ cis selectivity in glycosylation reactions. Using glycosyl donors with N ‐benzyl 2,3‐ trans carbamate groups, an anti‐ H elicobacter pylori oligosaccharide was synthesized in an efficient manner. Moreover, pyranosides with 2,3‐ trans carbamate groups readily undergo anomerization from the β to the α configuration under mild acidic conditions via endocyclic cleavage. Acyclic cations generated during the endocyclic cleavage reaction were captured using reduction and intramolecular F riedel– C rafts reaction. By exploiting this anomerization, multiply aligned 1,2‐ trans glycosyl bonds can be transformed to 1,2‐ cis glycosyl bonds in a single operation.