Gas-chromatographic approach to probe the absence of molecular inclusion in enantioseparations by carbohydrates. Investigation of linear dextrins ("acyclodextrins") as novel chiral stationary phases.
Acetylated/silylated maltooligosaccharides with different degrees of oligomerization have been tested as chiral stationary phases for enantioselective gas chromatography. The acyclic dextrin derivatives carrying tert-butyldimethylsilyl groups at the primary hydroxyl sites and acetyl groups at the secondary hydroxyl sites showed an unexpected ability for the enantioseparation of alpha-amino acid derivatives and halogenated compounds, in addition to some underivatized chiral compounds. Some examples of an improved enantioselectivity invoked by the linear CSPs as compared to that of cyclic oligosaccharides are demonstrated in this work. The results highlight the role of the polar external surface of the selector in lieu of the well-established inclusion mechanism of enantiorecognition by cyclic dextrins. Thus, the enantioseparation of chiral compounds on linear dextrin derivatives--devoid of a molecular cavity--sheds a new light on the mechanisms of enantiorecognition by cyclodextrin derivatives. In contrast to cyclodextrins, linear dextrins are readily accessible in both enantiomeric forms.
Sicoli
Giuseppe
G
Institut für Organische Chemie, Universität Tübingen, Auf der Morgenstelle 18, Tübingen, Germany.
Pertici
Francesca
F
Jiang
Zhengjin
Z
Jicsinszky
Lazslo
L
Schurig
Volker
V
D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D002849:Chromatography, Gas / Q000379:methods*; D003505:Cyclodextrins / Q000737:chemistry; D003912:Dextrins / Q000737:chemistry*; D008958:Models, Molecular; D008969:Molecular Sequence Data; D009844:Oligosaccharides / Q000737:chemistry; D013237:Stereoisomerism
D003505:Cyclodextrins; D003912:Dextrins; D009844:Oligosaccharides; C021705:maltooligosaccharides