M. Shizuma et al., Chiral discrimination of fructo-oligosaccharides toward amino acid derivatives by induced-fitting chiral recognition, J CHEM S P2, (4), 2001, pp. 592-601
Citations number
88
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2
Among linear permethylated fructo-oligosaccharides containing various monos
accharide moieties at the reducing terminal, MeSorFru(3), MeGlc(6)Fru(3), a
nd MeFruNys showed high degrees of enantioselectivity toward binding some a
mino acid 2-propyl ester salts. In particular MeFruNys indicated remarkable
chiral discrimination toward [ValOPr(i)](+) (I-R/IS-Dn = 0.14 correspondin
g to -Delta DeltaG(enan) = 1.2 kcal mol(-1), S-selectivity) and [PheOPr(i)]
(+) (I-R/IS-Dn = 0.18 corresponding to -Delta DeltaG(enan) = 1.0 kcal mol(-
1), S-selectivity). The results of FAB mass, UV-visible spectrometries, the
rmodynamic parameters, and NMR induced shifts provided evidence for the chi
ral discrimination of MeFruNys toward amino acid ester salts in the "induce
d-fitting chiral recognition system": the conformation of MeFruNys drastica
lly changes from a linear to a pseudo-ring structure with a given cation su
ch as a chiral organic ammonium ion or an alkali metallic ion. This is the
first example of chiral discrimination of linear oligosaccharide derivative
s toward amino acid derivatives based on the induced-fitting chiral recogni
tion mechanism.