title: Vibrational absorption and circular dichroism studies of (-)-camphanic acid.
abstract: Vibrational absorption and circular dichroism (VCD) spectra of (-)-(1S,3R)-camphanic acid have been measured in deuterated chloroform solutions at different concentrations (0.005, 0.045, and 0.200 M) in the mid-infrared spectral range. Experimental spectra have been compared with the density functional theory (DFT) absorption and VCD spectra, calculated using the B3PW91 functional and cc-pVTZ basis set for three conformers of both the monomer and the dimer forms of (-)-(1S,3R)-camphanic acid. These calculations indicate that, in the dilute solution, the conformer with intramolecular hydrogen-bonding between the hydroxyl and lactone groups is of lowest energy and represents 70% of the different monomer conformers at room temperature, whereas, in concentrated solution, the dimer formed by intermolecular hydrogen-bonding of carboxyl groups of the two distinct monomer conformations is stabilized. The vibrational absorption and circular dichroism spectra calculated from the Boltzmann population of the individual monomer and dimer conformers are in very good overall agreement with the corresponding experimental spectra, allowing the absolute conformation and configuration of (-)-(1S,3R)-camphanic acid in dilute and concentrated solution, respectively. Experiments were also performed on (-)-(1S,3R)-camphanic chloride for which the populations predicted by DFT calculations are found to be in disagreement with those deduced from experimental spectra.
authors.affiliation: Laboratoire de Physico-Chimie Moléculaire, UMR 5803 du CNRS, Université Bordeaux I, 351 Cours de la Libération, 33405 Talence, France. t.buffeteau@lpcm.u-bordeaux1.fr
authors.forename: Thierry
authors.initials: T
authors.lastname: Buffeteau
authors.forename: Dominique
authors.initials: D
authors.lastname: Cavagnat
authors.forename: Aude
authors.initials: A
authors.lastname: Bouchet
authors.forename: Thierry
authors.initials: T
authors.lastname: Brotin
mesh_terms: D001952:Bridged-Ring Compounds / Q000737:chemistry*; D002942:Circular Dichroism / Q000379:methods*; D006860:Hydrogen Bonding; D007783:Lactones / Q000737:chemistry*; D008968:Molecular Conformation; D012680:Sensitivity and Specificity; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods; D013237:Stereoisomerism; D014732:Vibration
chemical_list: D001952:Bridged-Ring Compounds; D007783:Lactones; C500772:camphanic acid