Gas-Chromatographic Enantioseparation of Unfunctionalized Chiral Hydrocarbons: An Overview

Abstract

Analytical gas-chromatographic enantioseparations of unfunctionalized chiral hydrocarbons (cycloalkanes and alkanes) on modified cyclodextrins with high-resolution capillary columns are reviewed. Due to the lack of functional groups of the hydrocarbons, enantiorecognition in the presence of cyclodextrins is ascribed to weak van der Waals forces. Thermodynamic parameters of enantiorecognition between four chiral alkanes and octakis(6-O-methyl-2,3-di-O-pentyl)-γ-cyclodextrin (Lipodex G) have been determined. The possible role of molecular inclusion is indicated by the complete loss of enantioselectivity when the cyclodextrins are replaced by the corresponding linear dextrins. The substitution pattern and cavity size of the modified cyclodextrins have a pronounced effect on the degree of enantiorecognition observed. On mixed binary cyclodextrin stationary phases, all C7 and C8 chiral alkanes possessing one stereogenic center can be enantioseparated simultaneously. The methodology has been used to determine enantiomeric excesses, ee, of alkanes formed by the enantioselective catalytic hydrogenation of prochiral alkenes. The novel online coupling of enantioselective gas chromatography with proton nuclear magnetic resonance spectroscopy is demonstrated for 2,4-dimethylhexane and Lipodex G.