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Revision of the Absolute Configurations of Chelocardin and Amidochelocardin |
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| Authors: | Dr Asfandyar Sikandar Dr Alexander Popoff Dr Ravindra P Jumde Dr Attila Mándi Dr Amninder Kaur Dr Walid A M Elgaher Dr Lara Rosenberger Dr Stephan Hüttel Dr Rolf Jansen Dr Maja Hunter Prof Dr Jesko Köhnke Prof Dr Anna K H Hirsch Prof Dr Tibor Kurtán Prof Dr Rolf Müller |
| Institution: | 1. Helmholtz Institute for Pharmaceutical Research Saarland (HIPS) -, Helmholtz Centre for Infection Research (HZI), Campus Building E8.1, 66123 Saarbrücken, Germany;2. Helmholtz Institute for Pharmaceutical Research Saarland (HIPS) -, Helmholtz Centre for Infection Research (HZI), Campus Building E8.1, 66123 Saarbrücken, Germany
These authors contributed equally to this work.;3. Department of Organic Chemistry University of Debrecen, P. O. Box 400, 4002 Debrecen, Hungary;4. Helmholtz Institute for Pharmaceutical Research Saarland (HIPS) -, Helmholtz Centre for Infection Research (HZI), Campus Building E8.1, 66123 Saarbrücken, Germany Department of Pharmacy, Saarland University, Campus Building E8.1, 66123 Saarbrücken, Germany Discovery and Development Technologies (DDTech), Merck KGaA, Frankfurter Strasse 250, 64293 Darmstadt, Germany;5. German Centre for Infection Research (DZIF), Partner Site Hannover-Braunschweig, 38124 Braunschweig, Germany Department of Microbial Drugs, Helmholtz Centre for Infection Research (HZI), 38124 Braunschweig, Germany;6. Helmholtz Institute for Pharmaceutical Research Saarland (HIPS) -, Helmholtz Centre for Infection Research (HZI), Campus Building E8.1, 66123 Saarbrücken, Germany School of Chemistry, University of Glasgow, University Avenue, Glasgow, G12 8QQ UK;7. Helmholtz Institute for Pharmaceutical Research Saarland (HIPS) -, Helmholtz Centre for Infection Research (HZI), Campus Building E8.1, 66123 Saarbrücken, Germany Department of Pharmacy, Saarland University, Campus Building E8.1, 66123 Saarbrücken, Germany Helmholtz International Lab for Anti-infectives, Campus Building E8.1, 66123 Saarbrücken, Germany |
| Abstract: | Even with the aid of the available methods, the configurational assignment of natural products can be a challenging task that is prone to errors, and it sometimes needs to be corrected after total synthesis or single-crystal X-ray diffraction (XRD) analysis. Herein, the absolute configuration of amidochelocardin is revised using a combination of XRD, NMR spectroscopy, experimental ECD spectra, and time-dependent density-functional theory (TDDFT)-ECD calculations. As amidochelocardin was obtained via biosynthetic engineering of chelocardin, we propose the same absolute configuration for chelocardin based on the similar biosynthetic origins of the two compounds and result of TDDFT-ECD calculations. The evaluation of spectral data of two closely related analogues, 6-desmethyl-chelocardin and its semisynthetic derivative 1 , also supports this conclusion. |
| Keywords: | Amidochelocardin Chelocardin Circular Dichroism Crystallography Stereochemistry |