title: Determination of the absolute configuration of chiral alpha-aryloxypropanoic acids using vibrational circular dichroism studies: 2-(2-chlorophenoxy) propanoic acid and 2-(3-chlorophenoxy) propanoic acid.
abstract: The enantiomers of 2-(2-chlorophenoxy) propanoic acid and 2-(3-chlorophenoxy) propanoic acid were resolved on a chiral HPLC column and investigated using mid-infrared vibrational circular dichroism (VCD). Experimental infrared vibrational absorption and VCD spectra were measured in CDCl3 solution in the 2000-900 cm-1 region and compared with the ab initio predictions of absorption and VCD spectra. The predicted spectra were obtained with density functional theory using B3LYP/6-31G* basis set for the stable and dominant conformers. But the predicted spectra did not provide unambiguous structural information due to intermolecular hydrogen bonding in solution. To eliminate the hydrogen bonding effects, the acids were converted to the corresponding methyl esters and the experimental absorbance and VCD spectra of methyl esters were measured. B3LYP predicted spectra were also obtained for the stable and dominant conformers of the esters. From a comparison of the experimental VCD spectra of methyl esters with corresponding ab initio predictions, the absolute configurations of esters, and therefore of their parent acids, are unambiguously determined to be (+)-(R).
authors.affiliation: Department of Chemistry, Vanderbilt University, Nashville, TN 37235, USA.
authors.forename: Jiangtao
authors.initials: J
authors.lastname: He
authors.forename: Prasad L
authors.initials: PL
authors.lastname: Polavarapu
mesh_terms: D002942:Circular Dichroism / Q000379:methods*; D004952:Esters; D006860:Hydrogen Bonding; D008956:Models, Chemical; D008958:Models, Molecular; D008962:Models, Theoretical; D008968:Molecular Conformation; D011422:Propionates / Q000737:chemistry*; D013053:Spectrophotometry / Q000379:methods; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D004952:Esters; D011422:Propionates