Vibrational Circular Dichroism of 1,1‘-Binaphthyl Derivatives:  Experimental and Theoretical Study

Abstract

Absorption and vibrational circular dichroism (VCD) spectra of six 1,1′-binaphthyl derivatives were measured and analyzed on the basis of ab initio modeling. The spectra of both enantiomers were recorded with a high signal-to-noise ratio. The BPW91/6-31G** density functional theory level and the gauge invariant atomic orbitals were used for the simulations of VCD intensities. The binaphthyl moiety behaves as a chiral chromophore with a strong VCD signal because the 1,1′-substitution hinders its rotation. Most of the VCD bands were assigned, and the contributions of the binaphthyl skeleton and the functional groups could be clearly distinguished. Distinct VCD characteristics were found for the compounds exhibiting C 2 and C 1 symmetry. A very good agreement between the calculated and experimental spectra was observed. Apart from indication of enantiomeric purity, the spectra contain readable information about molecular conformation. The dihedral angle between the naphthyls planes, equal to about 55°when naphthyl residues were connected with PO 4 covalent bridge, was found close to 90°for all the other derivatives.

Absolute configuration determination of chiral molecules in the solution state using vibrational circular dichroism

“…39 In a report from Switzerland on cinchona modifiers (cinchonidine, and (R)-2(pyrrolidin-1-yl)-1-(1-naphthyl)ethanol), VCD was observed and calculated for the carboxylate stretch of a nonchiral carboxylic acid bound to the alkaloids. 49 Several groups have investigated biphenyl or binaphthyl molecules with VCD, including four PCB-methylsulfone enantiomers (Germany), 50 several 1,1V binaphthyl derivatives (Czech Republic), 51 and from our group, the cotton derivative gossypol, 52 a D 2 -symmetric dimer of 1,1V-binaphthyl and a C 2 -symmetric annelated heptathiophene, 53 and (R,4S)-2-[4,5-dihydro-4-(1-methylethyl)oxazol-2-yl]-2V-hydroxymethyl-1,1V-biphenyl. 54 The VCD laboratory in the Czech Republic has also reported studies on (3R,4S)-4-(4-fluorophenyl)3-hydroxymethyl-1-methylpiperidine, 55 paroxetine and femoxetine precursors, 56 and twistbendanedione (tricyclo[4.3.0.0 3,8 ]nonane-4,5-dione).…”

Absorption, fluorescence, and cd spectroscopic study of chiral recognition by a binaphthyl‐derived chromogenic calixcrown host

“…24 Theoretical calculations suggest that the potential curve has a wide flat minimum around 90j, thus, Â can vary within a wide range in binaphthyl-derivatives, in accordance with the experimental findings. 25 The dihedral angle of f 80j in our compound means that the calix-crown chain linking the 1 and 1V positions of the naphthyl moieties leads only to a minor conformational distortion.…”

Elucidation of the absolute configuration of JNJ‐27553292, a CCR2 receptor antagonist, by vibrational circular dichroism analysis of two precursors

“…18 As these are not always available, the VCD of the solvent, measured in the same conditions as the sample, is often a good approximation. 19,20 For both the infrared and VCD spectra, there was no effect seen of possible self-association for compounds 3 and 5.…”