Stereochemical Assingment of β -lactam Antibiotics and their Analogues by Electronic Circular Dichroism Spectroscopy

Author(s): Magdalena Woznica, Patrycja Kowalska, Robert Lysek, Marek Masnyk, Marcin Gorecki, Marcin Kwit, Filipp Furche, Jadwiga Frelek.

Journal Name: Current Organic Chemistry

Volume 14 , Issue 10 , 2010

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Abstract:

The present work examines the relationship between the structure and chiroptical properties of penicillins and cephalosporins and their oxa- and carbaanalogues utilizing the electronic circular dichroism (CD). For some of the model compounds the study is additionally supported by the X-ray diffraction analysis. The applicability of the helicity rule that correlates the molecular structure of compounds and their CD spectra in respect to all classes of β-lactam derivatives is tested. It is demonstrated that a variety of oxacephams, clavams, and their carbaanalogues conform to the rule. To validate the experimental data the CD spectra computed using time-dependent density functional theory (TDDFT) are compared to the experimental curves recorded for the representative β-lactam derivatives. The study reveals a high sensitivity of the CD spectra to the configuration at the bridgehead atom and a surprisingly high sensitivity to the molecular conformation and substitution of the five- or six-membered ring. The results demonstrate that such a combined treatment permits the determination of the absolute configuration with high confidence.

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Article Details

VOLUME: 14
ISSUE: 10
Year: 2010
Page: [1022 - 1036]
Pages: 15
DOI: 10.2174/138527210791130497
Price: $58

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