Vibrational Circular Dichroism: A New Tool for the Solution-State Determination of the Structure and Absolute Configuration of Chiral Natural Product Molecules
Free accessResearch articleFirst published online March, 2008
Vibrational Circular Dichroism: A New Tool for the Solution-State Determination of the Structure and Absolute Configuration of Chiral Natural Product Molecules
Vibrational circular dichroism (VCD) has been used in recent years to determine the absolute configuration of a number of natural product chiral molecules. In this brief review, these applications will be described and the methodology of VCD determination of absolute configuration (AC) will be explained. The principal advantages of VCD versus X-ray crystallography for absolute configuration determination are: 1) only solution-state samples are needed and therefore single crystals are not required, 2) high enantiomeric sample purity is not required, 3) high chemical purity is not required as long as impurities are not chiral and 4) solution-state conformations are obtained as an extra feature of the AC determination.
BarronLD. (2004) Molecular Light Scattering and Optical Activity, Second Edition. Cambridge University Press, Cambridge.
2.
NafieLA. (1997) Infrared and Raman vibrational optical activity: theoretical and experimental aspects. Annual Review of Physical Chemistry, 48, 357–386.
3.
DukorRK, NafieLA. (2000) Vibrational Optical Activity of Pharmaceuticals and Biomolecules. In: MeyersRA. (Ed) Encyclopedia of Analytical Chemistry: Instrumentation and Applications. John Wiley and Sons, Chichester, 662–676.
NafieLA, DukorRK. (2007) Applications of Vibrational Optical Activity in the Pharmaceutical Industry. In: PivonkaD, ChalmersJM, GriffithsPR (Eds) Applications of Vibrational Spectroscopy in Pharmaceutical Research and Development. John Wiley & Sons, Ltd., Chichester, 129–154.
6.
StephensPJ, DevlinFJ. (2000) Determination of the structure of chiral molecules using ab initio vibrational circular dichroism spectroscopy. Chirality, 12, 172–179.
7.
StephensPJ (2003) Vibrational Circular Dichroism Spectroscopy: A New Tool for the Stereochmeical Characterization of Chiral Molecules. In: BultinckP, WinterHd, LangenaeckerW, TollenaereJ. (Eds) Computational Medicinal Chemistry for Drug Discovery. Dekker, New York, 699–725.
8.
FreedmanTB, CaoX, DukorRK, NafieLA. (2003) Absolute configuration determination of chiral molecules in the solution state using vibrational circular dichroism. Chirality, 15, 743–758.
9.
PolavarapuPL, HeJ. (2004) Chiral analysis using mid-IR vibrational CD spectroscopy. Analytical Chemistry, 76, 61A–67A.
10.
KuppensT, BultinckP, LangenaekerW. (2004) Determination of absolute configuration via vibrational circular dichroism. Drug Discovery Today: Technologies, 1, 269–275.
11.
PolavarapuPL. (2002) The absolute configuration of bromochlorofluoromethane. Angewandte Chemie, International Edition English, 41, 4544–4546.
12.
HaeslerJ, SchindelholzI, RiguetE, BochetCG, HugW. (2007) Absolute configuration of chirally deuterated neopentane. Nature (London, United Kingdom), 446, 526–529.
13.
HolzwarthG, HsuEC, MosherHS, FaulknerTR, MoscowitzA. (1974) Infrared circular dichroism of carbon-hydrogen and carbon-deuterium stretching modes. Observations. Journal of the American Chemical Society, 96, 251–252.
14.
NafieLA, ChengJC, StephensPJ. (1975) Vibrational circular dichroism of 2,2,2-trifluoro-1-phenylethanol. Journal of the American Chemical Society, 97, 3842–3843.
15.
BarronLD, BogaardMP, BuckinghamAD. (1973) Raman scattering of circularly polarized light by optically active molecules. Journal of the American Chemical Society, 95, 603–605.
16.
HugW, KintS, BaileyGF, SchererJR. (1975) Raman circular intensity differential spectroscopy. The spectra of (-)-α-pinene and (+)-α-phenylethylamine. Journal of the American Chemical Society, 97, 5589–5590.
CheD, HechtL, NafieLA. (1991) Dual and incident circular polarization Raman optical activity backscattering of (-)-trans-pinane. Chemical Physics Letters, 180, 182–190.
20.
YuG-S, NafieLA. (1994) Isolation of preresonance and out-of-phase dual circular polarization Raman optical activity. Chemical Physics Letters, 222, 403–410.
21.
KeiderlingTA, KubelkaJ, HilarioJ. (2006) Vibrational circular dichroism of biopolymers: summary of methods and applications. Vibrational Spectroscopy of Biological and Polymer Materials, 253–324.
22.
NafieLA, DiemM, VidrineDW. (1979) Fourier transform infrared vibrational circular dichroism. Journal of the American Chemical Society, 101, 496–498.
23.
NafieLA. (2000) Dual polarization modulation: a real-time, spectral-multiplex separation of circular dichroism from linear birefringence spectral intensities. Applied Spectroscopy, 54, 1634–1645.
24.
NafieLA, BuijsH, RillingA, CaoX, DukorRK. (2004) Dual source Fourier transform polarization modulation spectroscopy: An improved method for the measurement of circular and linear dichroism. Applied Spectroscopy, 58, 647–654.
25.
CaoX, ShahRD, DukorRK, GuoC, FreedmanTB, NafieLA. (2004) Extension of Fourier transform vibrational circular dichroism into the near-infrared region: Continuous spectral coverage from 800 to 10000 cm−1. Applied Spectroscopy, 58, 1057–1064.
26.
GuoC, ShahRD, DukorRK, FreedmanTB, CaoX, NafieLA. (2006) Fourier transform vibrational circular dichroism from 800 to 10,000cm-1: Near-IR-VCD spectral standards for terpenes and related molecules. Vibrational Spectroscopy, 42, 254–272.
27.
HugW, HangartnerG. (1999) A novel high-throughput Raman spectrometer for polarization difference measurements. Journal of Raman Spectroscopy, 30, 841–852.
28.
HugW. (2003) Virtual enantiomers as the solution of optical activity's deterministic offset problem. Applied Spectroscopy, 57, 1–13.
29.
HechtL, BarronLD, BlanchEW, BellAF, DayLA. (1999) Raman optical activity instrument for studies of biopolymer structure and dynamics. Journal of Raman Spectroscopy, 30, 815–825.
30.
HanzlikovaJ, PrausP, BaumrukV. (1999) Raman optical activity spectrometer for peptide studies. Journal of Molecular Structure, 480–481, 431–435.
31.
StephensPJ. (1985) Theory of vibrational circular dichroism. Journal of Physical Chemistry, 89, 748–752.
32.
StephensPJ. (1987) Gauge dependence of vibrational magnetic dipole transition moments and rotational strengths. Journal of Physical Chemistry, 91, 1712–1715.
33.
GalwasPA. (1983) On the distribution of optical polarization in molecules, Cambridge University, Ph.D. Thesis.
34.
BuckinghamAD, FowlerPW, GalwasPA. (1987) Velocity-dependent property surfaces and the theory of vibrational circular dichroism. Chemical Physics, 112, 1–14.
StephensPJ, PanJ-J, KrohnK. (2007) Determination of the absolute configurations of pharmacological natural products via density functional theory calculations of vibrational circular dichroism: The new cytotoxic iridoid prismatomerin. Journal of Organic Chemistry, 72, 7641–7649.
37.
StephensPJ, PanJ-J, DevlinFJ, UrbanovaM, HajicekJ (2007) Determination of the Absolute Configurations of Natural Products via Density Functional Theory Calculations of Vibrational Circular Dichroism, Electronic Circular Dichroism and Optical Rotation: The Schizozygane Alkaloid Schizozygine. Journal of Organic Chemistry, 72, 2508–2524.
38.
StephensPJ, PanJJ, DevlinFJ, KrohnK, KurtanT. (2007) Determination of the absolute configurations of natural products via density functional theory calculations of vibrational circular dichroism, electronic circular dichroism, and optical rotation: The iridoids plumericin and isoplumericin. Journal of Organic Chemistry, 72, 3521–3536.
39.
MinickDJ, CopleyRCB, SzewczykJR, RutkowskeRD, MillerLA. (2007) An investigation of the absolute configuration of the potent histamine H3 receptor antagonist GT-2331 using vibrational circular dichroism. Chirality, 19, 731–740.
40.
KuppensT, VandyckK, Van der EyckenJ, HerreboutW, van der VekenBJ, BultinckP. (2005) Determination of the absolute configuration of three as-hydrindacene compounds by vibrational circular dichroism. Journal of Organic Chemistry, 70, 9103–9114.
41.
KuppensT. (2006) Ph.D. Thesis, Ghent University, Development of methodology to assign absolute configurations using vibrational circular dichroism.
42.
DevlinFJ, StephensPJ, BesseP. (2005) Are the absolute configurations of 2-(1-hydroxyethyl)-chromen-4-one and its 6-bromo derivative determined by X-ray crystallography correct? A vibrational circular dichroism study of their acetate derivatives. Tetrahedron: Asymmetry, 16, 1557–1566.
43.
DevlinFJ, StephensPJ, CheesemanJR, FrischMJ. (1996) Prediction of vibrational circular dichroism spectra using density functional theory: Camphor and fenchone. Journal of the American Chemical Society, 118, 6327–6328.
44.
DevlinFJ, StephensPJ, CheesemanJR, FrischMJ. (1997) Ab initio prediction of vibrational absorption and circular dichroism spectra of chiral natural products using density functional theory: Camphor and fenchone. Journal of Physical Chemistry A, 101, 6322–6333.
45.
DevlinFJ, StephensPJ, CheesemanJR, FrischMJ. (1997) Ab initio prediction of vibrational absorption and circular dichroism spectra of chiral natural products using density functional theory: alpha.-pinene. Journal of Physical Chemistry A, 101, 9912–9924.
46.
FreedmanTB, CaoX, OliveiraRV, CassQB, NafieLA. (2003) Determination of the absolute configuration and solution conformation of gossypol by vibrational circular dichroism. Chirality, 15, 196–200.
47.
MondeK, TaniguchiT, MiuraN, NishimuraS-I, HaradaN, DukorRK, NafieLA. (2003) Preparation of cruciferous phytoalexin related metabolites, (-)-dioxibrassinin and (-)-3-cyanomethyl-3-hydroxyoxindole, and determination of their absolute configurations by vibrational circular dichroism (VCD). Tetrahedron Letters, 44, 6017–6020.
48.
BodackLA, FreedmanTB, ChowdhryBZ, NafieLA. (2004) Solution conformations of cyclosporins and magnesium-cyclosporin complexes determined by vibrational circular dichroism. Biopolymers, 73, 163–177.
49.
ShanmugamG, PolavarapuPL, GopinathD, JayakumarR. (2005) The structure of antimicrobial pexiganan peptide in solution probed by Fourier transform infrared absorption, vibrational circular dichroism, and electronic circular dichroism spectroscopy. Biopolymers, 80, 636–642.
50.
CichewiczRH, CliffordLJ, LassenPR, CaoX, FreedmanTB, NafieLA, DeschampsJD, KenyonVA, FlanaryJR, HolmanTR, CrewsP. (2005) Stereochemical determination and bioactivity assessment of (S)-(+)-curcuphenol dimers isolated from the marine sponge Didiscus aceratus and synthesized through laccase biocatalysis. Bioorganic & Medicinal Chemistry, 13, 5600–5612.
51.
LassenPR, SkytteDM, HemmingsenL, NielsenSF, FreedmanTB, NafieLA, ChristensenSB. (2005) Structure and absolute configuration of nyasol and hinokiresinol via synthesis and vibrational circular dichroism spectroscopy. Journal of Natural Products, 68, 1603–1609.
52.
MondeK, TaniguchiT, MiuraN, VairappanCS, SuzukiM. (2006) Absolute configurations of brominated sesquiterpenes determined by vibrational circular dichroism. Chirality, 18, 335–339.
53.
MondeK, TaniguchiT, MiuraN, VairappanCS, SuzukiM. (2006) Absolute configurations of endoperoxides determined by vibrational circular dichroism (VCD). Tetrahedron Letters, 47, 4389–4392.
54.
MunozMA, MunozO, Joseph-NathanP. (2006) Absolute configuration of natural diastereoisomers of 6β-hydroxyhyoscyamine by vibrational circular dichroism. Journal of Natural Products, 69, 1335–1340.
55.
Cerda-Garcia-RojasCM, Garcia-GutierrezHA, Hernandez-HernandezJD, Roman-MarinLU, Joseph-NathanP. (2007) Absolute configuration of verticillane diterpenoids by vibrational circular dichroism. Journal of Natural Products, 70, 1167–1172.
56.
KrautmannM, de RiscalaEC, Burgueno-TapiaE, Mora-PerezY, CatalanCA, Joseph-NathanP. (2007) C-15-Functionalized eudesmanolides Mikania campanulata. Journal of Natural Products, 70, 1173–1179.
57.
StephensPJ, McCannDM, DevlinFJ, SmithABIII., (2006) Determination of the absolute configurations of natural products via density functional theory calculations of optical rotation, electronic circular dichroism, and vibrational circular dichroism: The cytotoxic sesquiterpene natural products quadrone, suberosenone, suberosanone, and suberosenol A acetate. Journal of Natural Products, 69, 1055–1064.
58.
KrohnK, GehleD, DeySK, NaharN, MosihuzzamanM, SultanaN, SohrabMH, StephensPJ, PanJ-J, SasseF. (2007) Prismatomerin, a new iridoid from Prismatomeris tetrandra. Structure elucidation, determination of absolute configuration, and cytotoxicity. Journal of Natural Products, 70, 1339–1343.
59.
BercionS, BuffeteauT, LespadeL, CouppedeK.MartinM-A. (2006) IR, VCD, 1H and 13C NMR experimental and theoretical studies of a natural guaianolide: Unambiguous determination of its absolute configuration. Journal of Molecular Structure, 791, 186–192.
60.
MinHM, AyeM, TaniguchiT, MiuraN, MondeK, OhzawaK, NikaiT, NiwaM, TakayaY. (2007) A structure and an absolute configuration of (+)-alternamin, a new coumarin from Murraya alternans having antidote activity against snake venom. Tetrahedron Letters, 48, 6155–6158.
61.
AndersenNH, NielsJ.ChristensenLassen PR, FreedmanTB, NafieLA, StrømgaardK, HemmingsenL. Absolute configuration determination of ginkgolides by VCD spectroscopy, unpublished results.
62.
LassenPR. (2006) Ph.D. Thesis, Technical University of Denmark, Structural characterization of chiral molecules using vibrational circular dichroism spectroscopy.
63.
HeJ, PetrovicAG, DzyubaSV, BerovaN, NakanishiK, PolavarapuPL. (2007) Spectroscopic investigation of Ginko biloba terpene trilactones and their interaction with amyloid peptide Aβ (25–35). Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy doi: 10.1016/j.ssa.2007.06.030.
