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Synthesis, NMR, and Conformational Studies of Cyclic Oligo‐(1→6)‐β‐ D ‐Glucosamines
Author(s) -
Gening Marina L.,
Titov Denis V.,
Grachev Alexey A.,
Gerbst Alexey G.,
Yudina Olga N.,
Shashkov Alexander S.,
Chizhov Alexander O.,
Tsvetkov Yury E.,
Nifantiev Nikolay E.
Publication year - 2010
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200901275
Subject(s) - chemistry , glycosylation , intramolecular force , stereochemistry , bifunctional , glycosyl , glycosyl donor , proton nmr , acceptor , organic chemistry , biochemistry , physics , condensed matter physics , catalysis
The first synthesis of a series of homologous cyclic oligo‐(1→6)‐β‐ D ‐glucosamines consisting of two to seven residues and representing a new type of functionalized cyclic oligosaccharides is reported. Remarkably high yields of the studied macrocyclization reaction irrespective of the length of the acyclic precursors were observed. In the case of compounds constituted of four to seven glucosamine units α‐stereoisomers formed as side products despite the presence of a strongly participating 2‐ N ‐phthaloyl group to control β‐glycosylation. Both phenomena may be accounted for by conformational features of the linear bifunctional precursors. According to computer modeling and NMR conformational studies, the described linear (1→6)‐β‐linked oligoglucosamines exist in a right‐handed helix‐like conformation, in which the glycosyl donor and acceptor moieties are prearranged in a way that facilitates intramolecular glycosylation from the α‐side. Prepared cyclo‐oligoglucosamines differ in their conformational flexibilities, as illustrated by their spectral characteristics and calculated asphericity distributions. Moreover, the obtained compounds do not possess a distinct hydrophobic cavity, which is in contrast to the well‐known cyclodextrins. All these characteristics provide an excellent basis for the use of these novel cyclic oligosaccharides as scaffolds for the construction of biomolecular conjugates.