Determination of the Absolute Configurations Using Exciton Chirality Method for Vibrational Circular Dichroism: Right Answers for the Wrong Reasons?

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 119; no. 42; pp. 10589 - 10601
• Main Authors: Covington, Cody L, Nicu, Valentin P, Polavarapu, Prasad L
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 22.10.2015
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.5b07940

Quantum chemical (QC) predictions of vibrational circular dichroism (VCD) spectra for the keto form of 3-benzoylcamphor and conformationally flexible diacetates of spiroindicumide A and B are presented. The exciton chirality (EC) model has been briefly reviewed, and a procedure to evaluate the relevance of the EC model has been presented. The QC results are compared with literature experimental VCD spectra as well as with those obtained using the EC model for VCD. These comparisons reveal that the EC contributions to bisignate VCD couplets associated with the CO stretching vibrations of benzoylcamphor, spiroindicumide A diacetate, and spiroindicumide B diacetate are only ∼30%, ∼3%, and ∼15%, respectively. With such meager EC contributions, the correct absolute configurations (ACs) suggested in the literature for spiroindicumide A diacetate and spiroindicumide B diacetate molecules using the EC concepts can be considered fortuitous. The possibilities for obtaining wrong AC predictions using the EC concepts for VCD are identified, and guidelines for the future use of this model are presented.