Revised Absolute Configuration of Sibiricumin A: Substituent Effects in Simplified Model Structures Used for Quantum Mechanical Predictions of Chiroptical Properties

Abstract

This study discusses the choice of different simplified models used in computations of electronic circular dichroism (ECD) spectra and other chiroptical characteristics used to determine the absolute configuration (AC) of the complex natural product sibiricumin A. Sections of molecules containing one chiral center with one near an aromatic group have large effects on the ECD spectra. Conversely, when the phenyl group is present on a substituent without a nonstereogenic center, removal of this section will have little effect on ECD spectra. However, these nonstereogenic-center-containing sections have large effects on calculated optical rotations (OR) values since the OR value is more sensitive to the geometries of sections in a molecule. In this study, the wrong AC of sibiricumin A was reassigned as (7R,8S,1'R,7'R,8'S)-. Chirality 28:612-617, 2016. © 2016 Wiley Periodicals, Inc.