We report and discuss the infrared (IR) vibrational circular dichroism (VCD) spectra of the enantiomeric pairs of the olefin derivatives of fenchone (1,3,3-trimethyl-2-methylenebicyclo[2.2.1]heptane) and camphor (1,7,7-trimethyl-2-methylenebicyclo[2.2.1]heptane), respectively, together with those of the parent molecules. The VCD spectra were taken in three spectral regions: the mid-IR region, encompassing the fundamental deformation modes, the region of CH-stretching fundamental modes and the NIR-region between 1100 and 1300 nm, which corresponds to the second CH-stretching overtone. The VCD and absorption spectra in the first two regions are analyzed by use of current density functional theory (DFT) calculations. The NIR region is analyzed by a protocol that consists of the use of DFT-based calculations and in assuming local mode behavior: the local mode approach is found appropriate for interpreting the absorption spectra and, for the moment, acceptable for calculating NIR-VCD spectra. The analysis of the first region allows us to track the contribution of the C=O group in the vibrational optical activity of C-C stretching modes; notable differences are indeed found in olefins and ketones. On the contrary, in the other two regions the VCD spectra of olefins and ketones are more similar: in the normal mode region of CH stretching fundamentals the spectra are determined by the mutual orientation of the CH bonds; in the second overtone local mode region olefins and ketones signals show some differences.

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Near-infrared vibrational circular dichroism (VCD) spectra in the region 1500−850 nm are recorded for both enantiomers of camphor and fenchone using a home-built dispersive instrument. Two CH-stretching overtone regions and two CH-stretching/HCH-bending combination regions are investigated. The near-infrared VCD data are examined and compared with the corresponding previously published data of (3R)-(+)-methylcyclopentanone and (3R)-(+)-methylcyclohexanone. The absorption spectra of both the fundamental and overtone regions are also considered, and the fundamental CH-stretching VCD data are taken into account, where possible. An empirical assignment of the spectra is first considered, with special regard to the second CH-stretching overtone region. This region is then investigated by a heuristic approach based on DFT calculations, using the hybrid functional B3LYP at the 6-31G** basis set level. Subsequently rotational strengths have been evaluated by use of a classical model based on the contribution of polarizable groups to the optical activity. The same models are also used to interpret the VCD spectra between 2000 and 3000 wavenumbers for (3R)-(+)-methylcyclopentanone-d 4.