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Chiroptical Studies on Brevianamide B: Vibrational and Electronic Circular Dichroism Confronted

DOI: 10.1021/jo5022647 DOI Help

Authors: Patrick Bultinck (Ghent University) , Fanny L. Cherblanc (Imperial College London) , Matthew J. Fuchter (Imperial College London) , Wouter A. Herrebout (University of Antwerp) , Ya-pei Lo (Imperial College London) , Henry S. Rzepa (Imperial College London) , Giuliano Siligardi (Diamond Light Source) , Marko Weimar (Imperial College London)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: The Journal Of Organic Chemistry , VOL 80 (7) , PAGES 3359 - 3367

State: Published (Approved)
Published: April 2015
Diamond Proposal Number(s): 7994

Abstract: Chiroptical spectroscopies, such as electronic circular dichroism (ECD) and vibrational circular dichroism (VCD), are highly sensitive techniques to probe molecular conformation, configuration, solvation, and aggregation. Here we report the application of these techniques to study the fungal metabolite brevianamide B. Comparison of the experimental ECD and VCD spectra with the density functional theory simulated counterparts establishes that VCD is the more reliable technique to assign absolute configuration due to the larger functional and dispersion dependence of computed ECD spectra. Despite a low amount of available material and a relatively unusual example of using VCD carbonyl multiplets, the absolute configuration could be reliably predicted, strengthening the case for application of VCD in the study of complex natural products. Spectral and crystallographic evidence for or against the formation of a dimeric aggregate is discussed; in solution, the VCD spectra strongly suggest only monomeric species are present.

Subject Areas: Chemistry

Instruments: B23-Circular Dichroism