The Online Stereochemical Analysis of Chiral Compounds by HPLC‐ECD Coupling in Combination with Quantum‐Chemical Calculations

Bringmann, Gerhard; Götz, Daniel C. G.; Bruhn, Torsten

doi:10.1002/9781118120392.ch10

Cited by 14 publications

(11 citation statements)

References 77 publications

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“…The calculated ECD spectra were compared with the experimental ones by using SpecDis . For the calculation of the curves, a UV correction of −18 nm in combination with a spectral bandwidth σ of 0.20 eV was used.…”

Section: Methodsmentioning

confidence: 99%

Axially Chiral Dimeric Naphthalene and Naphthoquinone Metabolites, from Root Cultures of the West African LianaTriphyophyllum peltatum

et al. 2016

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Root cultures of the West African liana Triphyophyllum peltatum were initiated from stem explants of in vitro cultivated shoots. From these organ cultures, three new binaphthalenes, one binaphthoquinone, and two (bi)naphthalene glucosides were isolated, with substitution patterns related to those of the naphthylisoquinoline alkaloids, which are the "normal" main metabolites of T. peltatum. The structures of the diglucoside dioncoquinoside A (1) and of the axially chiral biaryls triphyoquinols A1 (3), A2 (4), and B (5), triphyoquinoside A (6), and triphyoquinone A (7) were elucidated by spectroscopic analysis (HRESIMS, 1D and 2D NMR) and by application of electronic circular dichroism (ECD) spectroscopy in combination with the exciton chirality method and quantum-chemical ECD calculations. The root cultures likewise produced the known alkaloids dioncophylline A (8), 5'-O-demethyldioncophylline A (9), dioncopeltine A (10), habropetaline A (11), and 5'-O-methyldioncophylline D (12a/b), the naphthalene glucoside plumbaside A (2), and the naphthoquinones plumbagin (13), droserone (14), and 8-hydroxydroserone (15).

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Section: Methodsmentioning

confidence: 99%

Axially Chiral Dimeric Naphthalene and Naphthoquinone Metabolites, from Root Cultures of the West African LianaTriphyophyllum peltatum

et al. 2016

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“…For example, ECD is not appropriate to elucidate the absolute configuration of molecules without a chromophore and is, in this respect, a little more limited than VCD or ROA. On the other hand, its advantage lies in the sensitivity of the method and in the possible hyphenation to HPLC so that small quantities or even components of complex mixtures can be analyzed online, by HPLC‐ECD, right from the peak in the chromatogram …”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, its advantage lies in the sensitivity of the method and in the possible hyphenation to HPLC so that small quantities or even components of complex mixtures can be analyzed online, by HPLC-ECD, right from the peak in the chromatogram. 2 There are already several reviews [3][4][5][6][7][8] (even in tutorial style 9 ) that describe how to calculate ECD spectra and which theoretical methods are most suited for certain classes of compounds. [10][11][12][13][14][15] Nevertheless, none of them describes in detail the process of comparing the measured and calculated spectra, and which considerations have to be taken into account to unambiguously determine the absolute configuration of a structure by ECD calculations without bias by subjective or even arbitrary criteria.…”

Section: Introductionmentioning

confidence: 99%

SpecDis: Quantifying the Comparison of Calculated and Experimental Electronic Circular Dichroism Spectra

et al. 2013

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This article outlines theory and practice of the comparison of calculated and experimental electronic circular dichroism (ECD) curves to determine the absolute configuration of chiral molecules. The focus is on the evaluation of excited-state calculations giving hints at the identification of the correct bandwidth and the application of the so-called "UV shift" as a correction factor. A similarity factor is introduced, which helps to quantify the degree of matching of curves. In addition, a few common errors are described that can be made during the measurements of ECD and UV spectra-and advice is given of how to avoid these mistakes. All equations mentioned in the article are implemented in our SpecDis software, which has been developed to rapidly compare calculated ECD and UV curves with experimental ones, and to produce graphics in publication quality.

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“…In the previous study, the acquisition of the ECD spectra was performed on the pure compounds but in the present case, we decided to turn to on-line detection in order to monitor the sign of the Cotton effect (CE) at 280 nm due to the minor amount of compounds present. This method has already been used for several natural products in the past, and proved highly efficient and sensitive [ 15 , 16 , 17 ].…”

Section: Resultsmentioning

confidence: 99%

Metabolome Consistency: Additional Parazoanthines from the Mediterranean Zoanthid Parazoanthus Axinellae

Audoin¹,

Cocandeau²,

Thomas

et al. 2014

Metabolites

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Ultra-high pressure liquid chromatography coupled to high resolution mass spectrometry (UHPLC-MS/MS) analysis of the organic extract obtained from the Mediterranean zoanthid Parazoanthus axinellae yielded to the identification of five new parazoanthines F-J. The structures were fully determined by comparison of fragmentation patterns with those of previously isolated parazoathines and MS/MS spectra simulation of in silico predicted compounds according to the metabolome consistency. The absolute configuration of the new compounds has been assigned using on-line electronic circular dichroism (UHPLC-ECD). We thus demonstrated the potential of highly sensitive hyphenated techniques to characterize the structures of a whole family of natural products within the metabolome of a marine species. Minor compounds can be characterized using these techniques thus avoiding long isolation processes that may alter the structure of the natural products. These results are also of interest to identify putative bioactive compounds present at low concentration in a complex mixture.

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The Online Stereochemical Analysis of Chiral Compounds by HPLC‐ECD Coupling in Combination with Quantum‐Chemical Calculations

Cited by 14 publications

References 77 publications

Axially Chiral Dimeric Naphthalene and Naphthoquinone Metabolites, from Root Cultures of the West African LianaTriphyophyllum peltatum

Axially Chiral Dimeric Naphthalene and Naphthoquinone Metabolites, from Root Cultures of the West African LianaTriphyophyllum peltatum

SpecDis: Quantifying the Comparison of Calculated and Experimental Electronic Circular Dichroism Spectra

Metabolome Consistency: Additional Parazoanthines from the Mediterranean Zoanthid Parazoanthus Axinellae

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