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.
Current Organic Chemistry
Title: Stereochemical Assingment of β -lactam Antibiotics and their Analogues by Electronic Circular Dichroism Spectroscopy
Volume: 14 Issue: 10
Author(s): Magdalena Woznica, Patrycja Kowalska, Robert Lysek, Marek Masnyk, Marcin Gorecki, Marcin Kwit, Filipp Furche and Jadwiga Frelek
Affiliation:
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.
Export Options
About this article
Cite this article as:
Woznica Magdalena, Kowalska Patrycja, Lysek Robert, Masnyk Marek, Gorecki Marcin, Kwit Marcin, Furche Filipp and Frelek Jadwiga, Stereochemical Assingment of β -lactam Antibiotics and their Analogues by Electronic Circular Dichroism Spectroscopy, Current Organic Chemistry 2010; 14 (10) . https://dx.doi.org/10.2174/138527210791130497
DOI https://dx.doi.org/10.2174/138527210791130497 |
Print ISSN 1385-2728 |
Publisher Name Bentham Science Publisher |
Online ISSN 1875-5348 |
Call for Papers in Thematic Issues
Advances of Heterocyclic Chemistry with Pesticide Activity
Global food safety and security will continue to be a global concern for the next 50 years and beyond. Plant diseases have had a significant impact on food safety and security throughout the entire food chain, from primary production to consumption. While conventional chemical pesticides have been traditionally used for ...read more
Calculation design of covalent/metal organic framework based catalysts
This research area combines theoretical computation and screening with machine learning for the design of covalent/metal organic framework-based catalysts, bridging the disciplines of organic chemistry, physical chemistry, computational chemistry, materials science, and machine learning. It covers several critical aspects: designing and synthesizing organic catalysts for improved performance, applying computational methods ...read more
Carbohydrates conversion in biofuels and bioproducts
Biomass pretreatment, hydrolysis, and saccharification of carbohydrates, and sugars bioconversion in biofuels and bioproducts within a biorefinery framework. Carbohydrates derived from woody biomass, agricultural wastes, algae, sewage sludge, or any other lignocellulosic feedstock are included in this issue. Simulation, techno-economic analysis, and life cycle analysis of a biorefinery process are ...read more
Catalytic C-H bond activation as a tool for functionalization of heterocycles
The major topic is the functionalization of heterocycles through catalyzed C-H bond activation. The strategies based on C-H activation not only provide straightforward formation of C-C or C-X bonds but, more importantly, allow for the avoidance of pre-functionalization of one or two of the cross-coupling partners. The beneficial impact of ...read more
Related Journals
- Author Guidelines
- Graphical Abstracts
- Fabricating and Stating False Information
- Research Misconduct
- Post Publication Discussions and Corrections
- Publishing Ethics and Rectitude
- Increase Visibility of Your Article
- Archiving Policies
- Peer Review Workflow
- Order Your Article Before Print
- Promote Your Article
- Manuscript Transfer Facility
- Editorial Policies
- Allegations from Whistleblowers
- Announcements