Assignment of the molecular absolute configuration through the ab initio Hartree-Fock calculation of the optical rotation: can the circular dichroism data help in reducing basis set requirements?

n this paper the calculation of the optical rotation (OR) of some rigid organic molecules, using the Hartree−Fock method with small (6-31G*, DZP) basis sets, has been studied thoroughly to carefully evaluate the scope and limitations of this method, previously introduced by other authors. Calculations on test molecules (compounds 1−13) together with a careful analysis of their CD spectra allow a simple criterion for the reliability of this approach to be formulated:  for unsaturated and/or aromatic (i.e., absorbing in the near-UV region) molecules, if the [α]D is quantitatively determined by the lowest energy Cotton effect (at wavelengths >220 nm), then the HF/6-31G* result is reliable. The usefulness of this method for the experimental organic chemist has been further demonstrated because the OR (sign and order of magnitude) of compounds 14−19 (i.e., large molecules having considerable interest in organic chemistry), which fulfill the above criterion and for which an extended basis set treatment is not feasible owing to their size, is correctly predicted.