Regular Article
SpecDis: Quantifying the Comparison of Calculated and Experimental Electronic Circular Dichroism Spectra
Torsten Bruhn,
Anu Schaumlöffel,
Yasmin Hemberger,
Gerhard Bringmann,
Corresponding Author
Torsten Bruhn
Institute of Organic Chemistry, University of Würzburg, Würzburg, Germany
Gerhard Bringmann or Torsten Bruhn, Institute of Organic Chemistry, University of Würzburg, Am Hubland, 97074 Würzburg, Germany. E-mail: [email protected], [email protected]Search for more papers by this authorAnu Schaumlöffel
Institute of Organic Chemistry, University of Würzburg, Würzburg, Germany
Search for more papers by this authorYasmin Hemberger
Institute of Organic Chemistry, University of Würzburg, Würzburg, Germany
Search for more papers by this authorCorresponding Author
Gerhard Bringmann
Institute of Organic Chemistry, University of Würzburg, Würzburg, Germany
Gerhard Bringmann or Torsten Bruhn, Institute of Organic Chemistry, University of Würzburg, Am Hubland, 97074 Würzburg, Germany. E-mail: [email protected], [email protected]Search for more papers by this authorTorsten Bruhn,
Anu Schaumlöffel,
Yasmin Hemberger,
Gerhard Bringmann,
Corresponding Author
Torsten Bruhn
Institute of Organic Chemistry, University of Würzburg, Würzburg, Germany
Gerhard Bringmann or Torsten Bruhn, Institute of Organic Chemistry, University of Würzburg, Am Hubland, 97074 Würzburg, Germany. E-mail: [email protected], [email protected]Search for more papers by this authorAnu Schaumlöffel
Institute of Organic Chemistry, University of Würzburg, Würzburg, Germany
Search for more papers by this authorYasmin Hemberger
Institute of Organic Chemistry, University of Würzburg, Würzburg, Germany
Search for more papers by this authorCorresponding Author
Gerhard Bringmann
Institute of Organic Chemistry, University of Würzburg, Würzburg, Germany
Gerhard Bringmann or Torsten Bruhn, Institute of Organic Chemistry, University of Würzburg, Am Hubland, 97074 Würzburg, Germany. E-mail: [email protected], [email protected]Search for more papers by this authorABSTRACT
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. Chirality 25:243–249, 2013. © 2013 Wiley Periodicals, Inc.
LITERATURE CITED
- 1 N Berova, RW Woody, P Polavarapu, K Nakanishi, editors. Comprehensive chiroptical spectroscopy. Hoboken: John Wiley & Sons; 2012.
- 2
Bringmann G,
Götz D,
Bruhn T. The online stereochemical analysis of chiral compounds by HPLC-ECD coupling in combination with quantum-chemical calculations. In: N Berova, RW Woody, P Polavarapu, K Nakanishi, editors. Comprehensive chiroptical spectroscopy. Vol. 2. Hoboken: John Wiley & Sons; 2012. p 355–386.
10.1002/9781118120392.ch10 Google Scholar
- 3 Warnke I, Furche F. Circular dichroism: electronic. WIREs Comput Mol Sci 2012; 2(1): 150–166.
- 4 Autschbach J, Ziegler T, van Gisbergen SJA, Baerends EJ. Chiroptical properties from time-dependent density functional theory. I. Circular dichroism spectra of organic molecules. J Chem Phys 2002; 116(16): 6930–6940.
- 5 Grimme S. Calculation of the electronic spectra of large molecules. In: KB Lipkowitz, R Larter, TR Cundari, editors. Reviews in computational chemistry. Vol. 20. Hoboken: John Wiley & Sons; 2004. p 153–218.
- 6 Crawford TD. Ab initio calculation of molecular chiroptical properties. Theo Chem Acc 2006; 115(4): 227–245.
- 7 Bringmann G, Bruhn T, Maksimenka K, Hemberger Y. The assignment of absolute stereostructures through quantum chemical circular dichroism calculations. Eur J Org Chem 2009(17): 2717–2727.
- 8 Pescitelli G, Kurtán T, Flörke U, Krohn K. Absolute structural elucidation of natural products—A focus on quantum-mechanical calculations of solid-state CD spectra. Chirality 2009; 21(1E): E181–E201.
- 9 Autschbach J. Computing chiroptical properties with first-principles theoretical methods: background and illustrative examples. Chirality 2009; 21(1E): E116–E152.
- 10 Jacquemin D, Perpete EA, Scuseria GE, Ciofini I, Adamo C. TD-DFT Performance for the visible absorption spectra of organic dyes: conventional versus long-range hybrids. J Chem Theory Comput 2008; 4(1): 123–135.
- 11 Jacquemin D, Wathelet V, Perpète EA, Adamo C. Extensive TD-DFT benchmark: singlet-excited states of organic molecules. J Chem Theory Comput 2009; 5(9): 2420–2435.
- 12 Goerigk L, Moellmann J, Grimme S. Computation of accurate excitation energies for large organic molecules with double-hybrid density functionals. Phys Chem Chem Phys 2009; 11(22): 4611–4620.
- 13 Goerigk L, Grimme S. Double-hybrid density functionals provide a balanced description of excited 1La and 1Lb states in polycyclic aromatic hydrocarbons. J Chem Theory Comput 2011; 7(10): 3272–3277.
- 14 Goerigk L, Grimme S. Assessment of TD-DFT methods and of various spin scaled CIS(D) and CC2 versions for the treatment of low-lying valence excitations of large organic dyes. J Chem Phys 2010; 132(18): 184103–184109.
- 15 Rudolph M, Autschbach J. Performance of conventional and range-separated hybrid density functionals in calculations of electronic circular dichroism spectra of transition metal complexes. J Phys Chem A 2011; 115(51): 14677–14686.
- 16 Bruhn T, Schaumlöffel A, Hemberger Y, Bringmann G. SpecDis version 1.53. Würzburg, Germany: University of Würzburg; 2012.
- 17www.organik.chemie.uniwuerzburg.de/lehrstuehlearbeitskreise/bringmann/specdis/
- 18www.gnuplot.info/
- 19 You L, Pescitelli G, Anslyn EV, Di Bari L. An exciton-coupled circular dichroism protocol for the determination of identity, chirality, and enantiomeric excess of chiral secondary alcohols. J Am Chem Soc 2012; 134(16): 7117–7125.
- 20 Allard PM, Martin MT, Tran Huu Dau ME, Leyssen P, Guéritte F, Litaudon M. Trigocherrin A, the first natural chlorinated daphnane diterpene orthoester from Trigonostemon cherrieri. Org Lett 2012; 14(1): 342–345.
- 21 Paululat T, Kulik A, Hausmann H, Karagouni AD, Zinecker H, Imhoff JF, Fiedler HP. Grecocyclines: new angucyclines from Streptomyces sp. Acta 1362. Eur J Org Chem. 2010; 2010(12): 2344–2350.
- 22 Masullo M, Bassarello C, Bifulco G, Piacente S. Polyisoprenylated benzophenone derivatives from the fruits of Garcinia cambogia and their absolute configuration by quantum chemical circular dichroism calculations. Tetrahedron 2010; 66(1): 139–145.
- 23 Funaioli T, Cavazza M, Zandomeneghi M, Pietra F. On the chiroptical behavior of conjugated multichromophoric compounds of a new pseudoaromatic class: bicolchicides and biisocolchicides. PLoS One 2010; 5(5): e10617.
- 24 Stephens PJ, Harada N. ECD cotton effect approximated by the Gaussian curve and other methods. Chirality 2010; 22(2): 229–233.
- 25 Kuppens T, Langenaeker W, Tollenaere JP, Bultinck P. Determination of the stereochemistry of 3-hydroxymethyl-2,3-dihydro-[1,4]dioxino[2,3-b]pyridine by vibrational circular dichroism and the effect of DFT integration grids. J Phys Chem A 2003; 107(4): 542–553.
- 26 Debie E, De Gussem E, Dukor RK, Herrebout W, Nafie LA, Bultinck P. A confidence level algorithm for the determination of absolute configuration using vibrational circular dichroism or Raman optical activity. Chem Phys Chem 2011; 12(8): 1542–1549.
- 27 Bifulco G, Dambruoso P, Gomez-Paloma L, Riccio R. Determination of relative configuration in organic compounds by NMR spectroscopy and computational methods. Chem Rev 2007; 107(9): 3744–3779.
- 28 Di Micco S, Chini MG, Riccio R, Bifulco G. Quantum mechanical calculation of NMR parameters in the stereostructural determination of natural products. Eur J Org Chem 2010; 2010(8): 1411–1434.
- 29 Schwabe T, Grimme S. Theoretical thermodynamics for large molecules: walking the thin line between accuracy and computational cost. Acc Chem Res 2008; 41(4): 569–579.
- 30 Pescitelli G, Di Bari L, Berova N. Conformational aspects in the studies of organic compounds by electronic circular dichroism. Chem Soc Rev 2011; 40: 4603–4625.
- 31 Kaye & Laby Online. Tables of Physical & Chemical Constants. 2.1.4 Hygrometry. Version 1.0 [2005]. Available from: www.kayelaby.npl.co.uk.
- 32 Yunt Z, Reinhardt K, Li A, Engeser M, Dahse H-M, Gütschow M, Bruhn T, Bringmann G, Piel J. Cleavage of four carbon-carbon bonds during biosynthesis of the griseorhodin A spiroketal pharmacophore. J Am Chem Soc 2009; 131(6): 2297–2305.
- 33 Polavarapu PL. Why is it important to simultaneously use more than one chiroptical spectroscopic method for determining the structures of chiral molecules? Chirality 2008; 20(5): 664–672.
- 34 Polavarapu PL. Molecular structure determination using chiroptical spectroscopy: where we may go wrong? Chirality 2012; 24: 909–920.
- 35 Loesgen S, Bruhn T, Meindl K, Dix I, Schulz B, Zeeck A, Bringmann G. (+)-Flavipucine, the missing member of the pyridione epoxide family of fungal antibiotics. Eur J Org Chem. 2011; 2011(26): 5156–5162.
- 36 Gussem ED, Bultinck P, Feledziak M, Marchand-Brynaert J, Stevens CV, Herrebout W. Vibrational circular dichroism versus optical rotation dispersion and electronic circular dichroism for diastereomers: the stereochemistry of 3-(1′-hydroxyethyl)-1-(3′-phenylpropanoyl)-azetidin-2-one. Phys Chem Chem Phys 2012; 14(24): 8562–8571.
- 37 Cherblanc F, Lo Y-P, De Gussem E, Alcazar-Fuoli L, Bignell E, He Y, Chapman-Rothe N, Bultinck P, Herrebout WA, Brown R, Rzepa HS, Fuchter MJ. On the determination of the stereochemistry of semisynthetic natural product analogues using chiroptical spectroscopy: desulfurization of epidithiodioxopiperazine fungal metabolites. Chem Eur J 2011; 17(42): 11868–11875.
