From relative to absolute configuration of complex natural products: Interplay between NMR, ECD, VCD, and ORD assisted by ab initio calculations

Current Organic Chemistry

Volumn 14, Issue 15, 2010, Pages 1612-1628

  Petrovic, Ana G ^a   Navarro Vázquez, Armando ^b   Alonso Gómez, José Lorenzo ^b  

^a Och Spine at New York Presbyterian Hospitals   (United States)

^b UNIVERSITY OF VIGO   (Spain)

Author keywords

Ab initio; Absolute configuration determination; Ecd; Natural products; Nmr; Ord; Relative configuration determination; Vcd

Indexed keywords

QUANTUM THEORY;

AB INITIO; ABSOLUTE CONFIGURATION; ABSOLUTE CONFIGURATION DETERMINATIONS; CONFIGURATION DETERMINATION; ECD; NATURAL PRODUCTS; NMR; ORD; RELATIVE CONFIGURATION DETERMINATION; VCD;

FORECASTING;

EID: 77956415052     PISSN: 13852728     EISSN: None     Source Type: Journal    
DOI: 10.2174/138527210793563215     Document Type: Article

References (162)

1. [1] Berger, S.; Sicker, D. In Classis in Spectroscopy: Isolation and Structure Elucidation of Natural Products; WILEY-VCH Verlag GmbH & Co. KGaA: 2009.
2. [2] Nicolaou, K. C.; Snyder, S. A. Chasing molecules that were never there: Misassigned natural products and the role of chemical synthesis in modern structure elucidation. Angew. Chem. Int. Ed. 2005, 44, 1012-1044.
3. Polavarapu, P. L. Renaissance in chiroptical spectroscopic methods for molecular structure determination. Chem. Rec. 2007, 7, 125-136.
4. Berova, N.; Di Bari, L.; Pescitelli, G. Application of electronic circular dichroism in configurational and conformational analysis of organic compounds. Chem. Soc. Rev. 2007, 36, 914-931.
5. Bringmann, G.; Bruhn, T.; Maksimenka, K.; Hemberger, Y. The assignment of absolute stereostructures through quantum chemical circular dichroism calculations. Eur. J. Org. Chem. 2009, 2717-2727.
6. Polavarapu, P. L. Protocols for the analysis of theoretical optical rotations. Chirality 2006, 18, 348-356.
7. Kellenbach, E. R.; Dukor, R. K.; Nafie, L. A. Absolute configuration determination of chiral molecules without crystallisation by vibrational circular dichroism (VCD). Spectrosc. Eur. 2007, 19, 15-17.
8. [8] Polavarapu, P. L.; He, J. A chiral analysis using mid-IR vibrational CD spectroscopy. Anal. Chem. 2004, 76, 61A-67A.
9. García, M. E.; Pagola, S.; Navarro-Vázquez, A.; Philips, D. D.; Gayathri, C.; Krakauer, H.; Stephens, P. W.; Nicotra, V.; Gil, R. R. Stereochemistry determination by powder X-Ray diffraction and NMR spectroscopy residual dipolar couplings. Angew. Chem. Int.Ed. 2009, 48, 5670-5674.
10. Schuetz, A.; Murakami, T.; Takada, N.; Junker, J.; Hashimoto, M.; Griesinger, C. RDC-enhanced NMR spectroscopy in structure elucidation of sucro-neolambertellin. Angew. Chem. Int. Ed. 2008, 47, 2032-2034.
11. Fares, C.; Hassfeld, J.; Menche, D.; Carlomagno, T. Simultaneous determination of the conformation and relative configuration of archazolide A by using nuclear Overhauser effects, J couplings, and residual dipolar couplings. Angew. Chem. Int. Ed. 2008, 47, 3722-3726.
12. 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, 3744-3779.
13. Riccio, R.; Bifulco, G.; Cimino, P.; Bassarello, C.; Gomez-Paloma, L. Stereochemical analysis of natural products. Approaches relying on the combination of NMR spectroscopy and computational methods. Pure Appl. Chem. 2003, 75, 295-308.
14. Seco, J. M.; Quinoa, E.; Riguera, R. The assignment of absolute configuration by NMR. Chem. Rev. 2004, 104, 17-117.
15. Nakanishi, K.; Berova, N.; Woody, R. W. Circular Dichroism: Principles and Applications. WILEY-VCH, New York 1994.
16. [16] Barron, L. D. In Molescular Light Scattering and Optical Activity; Cambridge University Press: Cambridge, 2004.
17. Autschbach, J. Computing chiroptical properties with first-principles theoretical methods: Background and illustrative examples Chirality 2009, 21, S116-S152.
18. Rubinstein, R. Y.; Kroese, D. P. In Simulation and the Monte Carlo Method; John Wiley & Sons.: New York, 2007, 341.
19. Metropolis, N.; Ulam, S. The Monte Carlo method. J. Am. Stat. Assoc. 1949, 44, 335-341.
20. Kirkpatrick, S.; Gelatt Jr., C. D.; Vecchi, M. P. Optimization by simulated annealing. Science 1983, 220, 671-680.
21. Metropolis, N.; Rosenbluth, A. W.; Rosenbluth, M. N.; Teller, A. H.; Teller, E. Equation of state calculations by fast computing machines. J. Chem. Phys. 1953, 21, 1087-1092.
22. Allinger, N. L.; Yuh, Y. H.; Lii, J. H. Molecular mechanics. The MM3 force field for hydrocarbons. J. Am. Chem. Soc. 1989, 111, 8551-8566.
23. Lii, J. H.; Allinger, N. L. Molecular mechanics. The MM3 force field for hydrocarbons. 3. The van der Waals' potentials and crystal data for aliphatic and aromatic hydrocarbons. J. Am. Chem. Soc. 1989, 111, 8576-8582.
24. Halgren, T. Merck molecular force field.1. Basis, form, scope, parameterization, and performance of MMFF94. J. Comput. Chem. 1996, 17, 490-519.
25. Halgren, T. Merck molecular force field.2. MMFF94 van der Waals and electrostatic parameters for intermolecular interactions. J. Comput. Chem. 1996, 17, 520-552.
26. Halgren, T. Merck molecular force field.3. Molecular geometries and vibrational frequencies for MMFF94. J. Comput. Chem. 1996, 17, 553-586.
27. Halgren, T.; Nachbar, R. Merck molecular force field.4. Conformational energies and geometries for MMFF94. J. Comput. Chem. 1996, 17, 587-615.
28. Halgren, T. Merck molecular force field.5. Extension of MMFF94 using experimental data, additional computational data, and empirical rules. J. Comput. Chem. 1996, 17, 616-641.
29. Damm, W.; Frontera, A.; Tirado-Rives, J.; Jorgensen, W. L. OPLS All-Atom force field for carbohydrates. J. Comp. Chem. 1997, 18, 1955-1970.
30. Jorgensen, W. L.; Maxwell, D. S.; Tirado-Rives, J. Development and testing of the OPLS All-Atom force field on conformational energetics and properties of organic liquids. J. Am. Chem. Soc. 1996, 118, 11225-11236.
31. Jorgensen, W. L.; Tirado-Rives, J. The OPLS [optimized potentials for liquid simulations] potential functions for proteins, energy minimizations for crystals of cyclic peptides and crambin. J. Am. Chem. Soc. 1988, 110, 1657-1666.
32. Rivera-Fuentes, P.; Alonso-Gómez, J. L.; Petrovic, A.; Santoro, F.; Harada, N.; Berova, N.; Diederich F. Amplification of chirality in monodisperse, enantiopure alleno-acetylenic oligomers. Angew. Chem. Int. Ed. 2010, 49, 2247-2250.
33. Clerc, J. T.; Sommerauer, H. A minicomputer program based on additivity rules for the estimation of 13c-nmr chemical shifts. Anal. Chim. Acta 1977, 95, 33-40.
34. Pretsch, E.; Fürst, A. A computer program for the prediction of 13C-NMR chemical shifts of organic compounds. Anal. Chim. Acta 1990, 229, 17-25.
35. Chen, L. R.; Robien, W. OPSI: A universal method for prediction of 13C- NMR spectra based on optimized additivity models. Anal. Chem. 1993, 65, 2282-2287.
36. Bremser, W. HOSE, A novel structure code. Anal. Chim. Acta 1978, 103, 355-365.
37. Meiler, J.; Meusinger, R.; Will, M. Fast determination of 13C NMR chemical shifts using artificial neural networks. J. Chem. Inf. Comput. Sci. 2000, 40, 1169-1176.
38. Blinov, K. A.; Smurnyy, Y. D.; Elyashberg, M. E.; Churanova, T. S.; Kvasha, M.; Steinbeck, C.; Lefebvre, B. A.; Wiliams, A. J. Performance validation of neural network based C-13 NMR prediction using a publicly available data source. J. Chem. Inf. Model 2008, 48, 550-555.
39. Altona, C. In Vicinal Coupling Constants & Conformation of Biomolecules. Encyclopedia of NMR; Grant, D. M., Morris, R., Eds.; Wiley: New York, 1996; 4909-4923.
40. Karplus, M. Vicinal proton coupling in nuclear magnetic resonance. J. Am. Chem. Soc. 1963, 85, 2870-2871.
41. Haasnoot, C. A. G.; de Leeuw, F. A. A. M.; Altona, C. The relationship between proton-proton NMR coupling constants and substituent electronega- tivities-I. An empirical generalization of the karplus equation. Tetrahedron 1980, 36, 2783-2792.
42. Navarro-Vazquez, A.; Carlos, J. C.; Sardina, F. J.; Casanueva, J.; Diez, E. A graphical tool for the prediction of vicinal proton-proton 3JHH coupling con- stants. J. Chem. Inf. Comput. Sci. 2004, 44, 1680-1685.
43. Helgaker, T.; Jaszunski, M.; Ruud, K. Ab initio methods for the calculation of NMR shielding and indirect spin-spin coupling constants. Chem. Rev. 1999, 99, 293-352.
44. Helgaker, T.; Jaszu ski, M.; Pecul, M. The quantum-chemical calculation of NMR indirect spin-spin coupling constants. Prog. Nucl. Magn. Reson. Spectrosc. 2008, 53, 249-268.
45. [45] Bassarello, C.; Cimino, P.; Gomez-Paloma, L.; Riccio, R.; Bifulco, G. Recent acquisitions in the resolution of structural problems by NMR and quantum mechanical methods. Recent Res. Dev. Org. Chem. 2003, 7, 219-239.
46. 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, 3744-3779.
47. Bagno, A.; Saielli, G. Computational NMR spectroscopy: Reversing the information flow. Theor. Chem. Accounts 2007, 117, 603-619.
48. Cheeseman, J. R.; Trucks, G. W.; Keith, T. A. Frisch, M. J. A comparison of models for calculating nuclear magnetic resonance shielding tensors. J. Chem. Phys. 1996, 104, 5497-5509.
49. Wolinski, K.; Hinton, J. F.; Pulay, P. Efficient implementation of the gauge- independent atomic orbital method for NMR chemical shift calculations. J. Am. Chem. Soc. 1990, 112, 8251-8260.
50. [50] Ditchfield, R. Self-Consistent perturbation-theory of diamagnetism. gauge- invariant LCAO method for NMR chemical-shifts. Mol. Phys. 1974, 27, 789-807.
51. Keith, T. A.; Bader, R. F. W. Calculation of magnetic response properties using a continuous set of gauge transformations. Chem. Phys. Lett. 1993, 210, 223-231.
52. Wu A., Zhang Y., Xu X., Yan Y., Systematic studies on the computation of nuclear magnetic resonance shielding constants and chemical shifts: the density functional models. J. Comput. Chem. 2007, 28, 2431-2442.
53. Koch, W.; Holthausen, M. C. In A Chemist's guide to Density Functional Theory; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, 2001.
54. Lee, A.; Handy, N.; Colwell, S. M. The density-functional calculation of nuclear shielding constants using london atomic orbitals. J. Chem. Phys. 1995, 103, 10095-10109.
55. Wiitala, K. W.; Hoye, T. R.; Cramer, C. J. Hybrid density functional methods empirically optimized for the computation of 13C and 1H chemical shifts in chloroform solution. J. Chem. Theory Comput. 2006, 2, 1085-1092.
56. Keal, T. W.; Tozer, D. J. The exchange-correlation potential in Kohn-Sham nuclear magnetic resonance shielding calculations. J. Chem. Phys. 2003, 119, 3015-3024.
57. Allen, M. J.; Keal, T. W.; Tozer, D. J. Improved NMR chemical shifts in density functional theory. Chem. Phys. Lett. 2003, 380, 70-77.
58. Zhang, Y.; Wu, A.; Xu, X.; Yan, Y. OPBE: A promising density functional for the calculation of nuclear shielding constants. Chem. Phys. Lett. 2006 421, 383-388.
59. Zhao, Y.; Truhlar, D. G. Letter improved description of nuclear magnetic resonance chemical shielding constants using the M06-L Meta-Generalized- gradient-approximation density functional. J. Phys. Chem. A 2008, 112, 6794-6799.
60. Van Voorhis, T.; Scuseria, G. E. A novel form for the exchange-correlation energy functional. J. Chem. Phys. 1998, 109, 400-410.
61. Ramsey, N. Electron coupled interactions between nuclear spins in molecules. Phys. Rev. 1953, 91, 303-307.
62. Manninen, P.; Vaara, J. Systematic gaussian basis-set limit using completeness-optimized primitive sets. A case for magnetic properties. J. Comp. Chem. 2006, 27, 434-445.
63. Jensen, F. Basis set convergence of nuclear magnetic shielding constants calculated by density functional methods. J. Chem. Theory Comput. 2008, 4, 719-727.
64. Jensen, F. The basis set convergence of spin-spin coupling constants calculated by density functional methods. J. Chem. Theory Comput. 2006, 2, 1360-1369.
65. Deng, W.; Cheeseman, J.; Frisch, M. Calculation of nuclear spin-spin coupling constants of molecules with first and second row atoms in study of basis set dependence. J. Chem. Theory Comput. 2006, 2, 1028-1037.
66. Zhao, Y.; Truhlar, D. Density functionals with broad applicability in chemistry. Acc. Chem. Res. 2008, 41, 157-167.
67. Tomasi, J.; Mennucci, B.; Cammi, R. Quantum mechanical continuum solvation models. Chem. Rev. 2005, 105, 2999-3093.
68. Dybiec, K.; Gryff-Keller, A. Remarks on GIAO-DFT predictions of 13 C chemical shifts. Magn. Reson. Chem. 2009, 47, 63-66.
69. Tousek, J.; Van Miert, S.; Pieters, L. Van Baelen, G.; Hostyn, S.; Maes, B. U. W.; Lemiere, G. M.; Dommise, R.; Marek, R. Structural and solvent effects on the 13C and 15N NMR chemical shifts of indoloquinoline alkaloids: Experimental and DFT study. Magn. Reson. Chem. 2008, 46, 42-51.
70. Bagno, A.; Rastrelli, F.; Saielli, G. Prediction of the 1H and 13C NMR spectra of []-d-Glucose in water by DFT methods and MD simulations. J. Org. Chem. 2007, 72, 7373-7381.
71. Sarotti, A. M.; Pellegrinet, S. C. A Multi-standard approach for GIAO C-13 NMR calculations. J. Org. Chem. 2009, 74, 7254-7260.
72. Braddock, D.; Rzepa, H. Structural reassignment of obtusallenes V, VI, and VII by GIAO-based density functional. J. Nat. Prod. 2008, 71, 728-730.
73. Kaupp, M.; Malkina, O.; Malkin, V.; Pyykkö, P. How do spin-orbit-induced heavy-atom effects on NMR chemical shifts function? validation of a simple analogy to spin-spin coupling by density functional theory (DFT) calculations on some iodo compounds. Chem. Eur. J. 1998, 4, 118-126.
74. Forsyth, D.; Sebag, A. Computed 13C NMR chemical shifts via empirically scaled GIAO shieldings. J. Am. Chem. Soc. 1997, 119, 9483-9494.
75. Giesen, D.; Zumbulyadis, N. A hybrid quantum mechanical and empirical model for the prediction of isotropic C-13 shielding constants of organic molecules. Phys. Chem. Chem. Phys. 2002, 4, 5498-5507.
76. Blanco, F.; Alkorta, I.; Elguero, J. Statistical analysis of 13C and 15N NMR chemical shifts from GIAO/B3LYP/6-311++ G** calculated absolute shieldings. Magn. Reson. Chem. 2007, 45, 797-800.
77. Smith, S. G.; Goodman, J. M. Assigning the stereochemistry of pairs of diastereoisomers using GIAO NMR shift calculation. J. Org. Chem. 2009, 74, 4597-4607.
78. Bagno, A.; Rastrelli, F.; Saielli, G. Toward the complete prediction of the 1H and 13C NMR spectra of complex organic molecules by DFT methods: application to natural substances. Chem. Eur. J. 2006, 12, 5514-5525.
79. Schlegel, B.; Härtl, A.; Dahse, H. M.; Gollmick, F. A.; Gräfe, U.; Dörfelt, H.; Kappes, B. Hexacyclinol, a new antiproliferative metabolite of panus rudis HKI 0254. J. Antibiot. 2002, 55, 814-817.
80. Clair, J. L. Total syntheses of hexacyclinol, 5-epi-hexacycyclinol, and desoxohexacyclinol unveil an antimalarial prodrug motif. Angew. Chem. Int.Ed. 2006, 45, 2769-2773.
81. [81] Rychnovsky, S. D. Predicting NMR spectra by computational methods: structure revision of hexacyclinol. Org. Lett. 2006, 13, 2895-2898
82. Porco Jr., J. A.; Su, S.; Lei, X.; Bardhan, S.; Rychnovsky, S. D. Total synthesis and structure assignment of (+)-hexacyclinol. Angew. Chem. Int.Ed. 2006, 45, 5790-5792.
83. Saielli, G.; Bagno, A. Can two molecules have the same NMR spectrum? Hexacyclinol revisited. Org. Lett. 2009, 11, 1409-1412.
84. Timmons, C.; Wipf, P. Density functional theory calculation of C-13 NMR shifts of diazaphenanthrene alkaloids: reinvestigation of the structure of samoquasine A. J. Org. Chem. 2008, 73, 9168-9170.
85. Hu, G.; Liu, K.; Williams, L. J. The brosimum allene: a structural revision. Org. Lett. 2008, 10, 5493-5496.
86. Xiao, W-L.; Lei, C.; Ren, J.; Liao, T-G.; Pu, J-X.; Pittman, Jr. C. U.; Lu, Y.; Zheng, Y-T.; Zhu, H-J.; Sun, H-D. Structure elucidation and theoretical in- vestigation of key steps in the biogenetic pathway of schisanartane nortriterpenoids by using DFT methods. Chem. Eur. J. 2008, 14, 11584-11592
87. Chini, M. G.; Riccio, R.; Bifulco, G. DFT/NMR integrated approach: a valid support to the total synthesis of chiral molecules. Magn. Reson. Chem. 2008, 46, 962-968.
88. Köck, M.; Grube, A.; Seiple, I. B.; Baran, P. S. The pursuit of Palau'amine. Angew. Chem. Int.Ed. 2007, 46, 6586-6594.
89. Seiple, I. B.; Su, S.; Young, I. S.; Lewis, C. A.; Yamaguchi, J.; Baran, P. S. Total synthesis of Palau ́amine. Angew. Chem. Int.Ed. 2010, 49, 1095-1098.
90. Stappen, I.; Buchbauer, G.; Robien, W.; Wolschann, P. 13C-NMR spectra of santalol derivatives: a comparison of DFT-Based calculations and database- oriented prediction techniques. Magn. Reson. Chem. 2009, 47, 720-726.
91. Sánchez-Pedregal, V. M.; Santamaría-Fernández, R.; Navarro-Vázquez, A. Residual dipolar couplings of freely rotating groups in small molecules. stereochemical assignment and side-chain conformation of 8-Phenylmenthol. Org. Lett. 2009, 11, 1471-1474.
92. Subramaniam, G.; Karimi, S.; Phillips, D. Solution conformation of longi- folene and its precursor by NMR and ab initio calculations. Magn. Reson. Chem. 2006, 44, 1118-1121.
93. [93] Muñoz, M. A.; Joseph-Nathan, P. DFT-GIAO 1H and 13C NMR prediction of chemical shifts for the configurational assignment of 6- hydroxyhyoscyamine diastereoisomers. Magn. Reson. Chem. 2009, 47, 578-584.
94. Wiitala, K. W.; Cramer, C. J.; Hoye, T. R. Comparison of various density functional methods for distinguishing stereoisomers based on computed 1H or 13C NMR chemical shifts using diastereomeric penam -lactams as a test set. Magn. Reson. Chem. 2007, 45, 819-829.
95. Fattorusso, C.; Stendardo, E.; Appendino, G.; Fattorusso, E.; Luciano, P.; Romano, A.; Taglialatela-Scafati, O. Artarborol, a Nor-caryophyllane Ses- quiterpene alcohol from artemisia arborescens. stereostructure assignment through concurrence of NMR data and computational analysis. Org. Lett. 2007, 9, 2377-2380.
96. Schellman, J. A. Symmetry rules for optical rotation. Acc. Chem. Res. 1968, 1, 144-151.
97. Polavarapu, P. L.; Petrovic, A.; Wang, F. Intrinsic rotation and molecular structure. Chirality 2003, 15, S143-S149.
98. Polavarapu, P. L. Ab initio molecular optical rotations and absolute configurations. Mol. Phys. 1997, 91, 551-554.
99. Polavarapu, P. L.; Zhao, C. A Comparison of ab initio optical rotations obtained with static and dynamic methods. Chem. Phys. Lett. 1998, 296, 105-110.
100. Kondru, R. K.; Wipf, P.; Beratan, D. N. Theory-assisted determination of absolute stereochemistry for complex natural products via computation of molar rotation angles. J. Am. Chem. Soc. 1998, 120, 2204-2205.
101. Giorgio, E.; Minichino, C.; Viglione, R. G.; Zanasi, R.; Rosini, C. Assignment of the molecular absolute configuration through the ab initio hartree- fock calculation of the optical rotation: can the circular dichroism data help in reducing basis set requirements? J. Org. Chem. 2003, 68, 5186-5192.
102. Autschbach, J.; Patchkovskii, S.; Ziegler, T.; Van Gisbergen, S. J. A.; Baer ends, E. J. Chiroptical properties from time-dependent density functional theory. II: optical rotations of small to medium sized organic molecules. J. Chem. Phys. 2002, 117, 581-592.
103. Grimme, S. Calculation of frequency dependent optical rotation using density functional response theory. Chem. Phys. Lett. 2001, 339, 380-388.
104. Krykunov, M.; Autschbach, J. Calculation of optical rotation with time- periodic magnetic-field-dependent basis functions in approximate time- dependent density-functional theory. J. Chem. Phys. 2005, 123, 114103.
105. Stephens, P. J.; Devlin, F. J.; Cheeseman, J. R.; Frisch, M. J. Calculation of optical rotation using density functional theory. J. Phys. Chem. A 2001, 105, 5356-5371.
106. Yabana, K.; Bertsch, G. F. Application of the time-dependent local density approximation to optical activity. Phys. Rev. A 1999, 60, 1271-1279.
107. Pedersen, T. B.; Koch, H.; Boman, L.; Sánchez De Merás, A. M. J. Origin invariant calculation of optical rotation without recourse to london orbitals. Chem. Phys. Lett. 2004, 393, 319-326.
108. Ruud, K.; Stephens, P. J.; Devlin, F. J.; Taylor, P. R.; Cheeseman, J. R.; Frisch, M. J. Coupled-cluster calculations of optical rotation. Chem. Phys. Lett. 2003, 373, 606-614.
109. Tam, M. C.; Russ, N. J.; Crawford, T. D. Coupled cluster calculations of optical rotatory dispersion of (S)-Methyloxirane. J. Chem. Phys. 2004, 121, 3550-3557.
110. Pecul, M.; Ruud, K.; Helgaker, T. Density functional theory calculation of electronic circular dichroism using london orbitals. Chem. Phys. Lett. 2004, 388, 110-119.
111. Crassous, J.; Jiang, Z.; Schurig, V.; Polavarapu, P. L. Preparation of (+)- chlorofluoroiodomethane, determination of its enantiomeric excess and of its absolute configuration. Tetrahedron Asymmetry 2004, 15, 1995-2001.
112. Crawford, T. D.; Owens, L. S.; Tam, M. C.; Schreiner, P. R.; Koch, H. Ab initio calculation of optical rotation in (P)-(+)-[4] Triangulane. J. Am. Chem. Soc. 2005, 127, 1368-1369.
113. Polavarapu, P. L. The absolute configuration of bromochlorofluoromethane. Angew. Chem. Int.Ed. 2002, 41, 4544-4546.
114. Rinderspacher, B. C.; Schreiner, P. R. Structure-property relationships of prototypical chiral compounds: case studies. J. Phys. Chem. A 2004, 108, 2867-2870.
115. Specht, K. M.; Nam, J.; Ho, D. M. Determining absolute configuration in flexible molecules: a case study. J. Am. Chem. Soc. 2001, 123, 8961-8966.
116. Olsen, J.; Jørgensen, P. Time-dependent response theory with applications to self-consistent field and multiconfigurational self-consistent field wave functions. Modern Electron. Struct. Theory 1995, 2, 857-990.
117. Giorgio, E.; Viglione, R. G.; Zanasi, R.; Rosini, C. Ab Initio calculation of optical rotatory dispersion (ORD) curves: a simple and reliable approach to the assignment of the molecular absolute configuration. J. Am. Chem. Soc. 2004, 126, 12968-12976.
118. Bauernschmitt, R.; Ahlrichs, R. Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory. Chem. Phys. Lett. 1996, 256, 454-464.
119. Furche, F.; Ahlrichs, R. Absolute configuration of D2-Symmetric fullerene C84. J. Am. Chem. Soc. 2002, 124, 3804-3805.
120. Lackowski, K. Z.; Baranowska, A. Conformational analysis and optical rotation of carene -Amino alcohols: A DFT study. Eur. J. Org. Chem. 2009, 4600-4605.
121. Kwit, M.; Rozwadowska, M. D.; Gawro ski, J.; Grajewska, A. Density Functional theory calculations of the optical rotation and electronic circular dichroism: the absolute configuration of the highly flexible trans- isocytoxazone revised. J. Org. Chem. 2009, 74, 8051-8063.
122. Becke, A. D. Density-functional exchange-energy approximation with correct asymptotic behavior. Phys. Rev. A 1988, 38, 3098-3100.
123. Lee, C.; Yang, W.; Parr, R. G. Development of the Colle-Salvetti correlation- energy formula into a functional of the electron density. Phys. Rev. B 1988, 37, 785-789.
124. Cheeseman, J. R.; Frisch, M. J.; Devlin, F. J.; Stephens, P. J. Hartree-Fock and density functional theory ab initio calculation of optical rotation using giaos: basis set dependence. J. Phys. Chem. A 2000, 104, 1039-1046.
125. Stephens, P. J.; Devlin, F. J.; Cheeseman, J. R.; Frisch, M. J.; Mennucci, B.; Tomasi, J. Prediction of optical rotation using density functional theory: 6,8- Dioxabicyclo[3.2.1]octanes. Tetrahedron Asymmetry 2000, 11, 2443-2448.
126. Mennucci, B.; Tomasi, J.; Cammi, R. Polarizable continuum model (PCM) calculations of solvent effects on optical rotations of chiral molecules. J. Phys. Chem. 2002, 106, 6102-6113.
127. Stephens, P. J.; McCann, D. M.; Cheeseman, J. R.; Frisch, M. J. Determination of Absolute Configurations Of Chiral Molecules Using Ab Initio Time- Dependent Density Functional Theory Calculations Of Optical Rotation: How Reliable Are Absolute Configurations Obtained For Molecules With Small Rotations? Chirality 2005, 17, S52-S64.
128. London, F. Théorie quantique des courants interatomiques dans les combinaisons aromatiques. J. Phys. Radium 1937, 8, 397-409.
129. Clark, T.; Chandrasekhar, J.; Spitznagel, G. W.; Schleyer, P. V. R. Efficient diffuse function-augmented basis sets for anion calculations. III. The 3-21+G basis set for first-row elements, Li-F. J. Comput. Chem. 1983, 4, 294-301.
130. Frisch, M. J.; Pople, J. A.; Binkley, J. S. Self-Consistent molecular orbital methods 25. supplementary functions for gaussian basis sets. J. Chem. Phys. 1984, 80, 3265-3269.
131. Gill, P. M. W.; Johnson, B. G.; Pople, J. A.; Frisch, M. J. The performance of the Becke-Lee-Yang-Parr (B-LYP) density functional theory with various basis sets. Chem. Phys. Lett. 1992, 197, 499-505.
132. Krishnan, R.; Binkley, J. S.; Seeger, R.; Pople, J. A. Self-consistent molecular orbital methods. XX. a basis set for correlated wave functions. J. Chem. Phys. 1980, 72, 650-654.
133. McLean, A. D.; Chandler, G. S. Contracted gaussian basis sets for molecular calculations. I. second row atoms, Z=11-18. J. Chem. Phys. 1980, 72, 5639-5648.
134. Crawford, T. D.; Stephens, P. J. Comparison of time-dependent density- functional theory and coupled cluster theory for the calculation of the optical rotations of chiral molecules. J. Phys. Chem. A 2008, 112, 1339-1345.
135. Elguero, J.; Marzin, C.; Katritzky, A. R.; Linda, P. The Tautomerism of Heterocycles. Adv. Heterocycl. Chem. 1976, Suppl. 1.
136. Jia, L.; Shafirovich, V.; Shapiro, R.; Geacintov, N. E.; Broyde, S. Spiroimi- nodihydantoin lesions derived from guanine oxidation: structures, energetics, and functional implications. Biochemistry (N. Y.) 2005, 44, 6043-6051.
137. Durandin, A.; Jia, L.; Crean, C. Assignment of absolute configurations of the enantiomeric spiroiminodihydantoin nucleobases by experimental and computational optical rotatory dispersion methods. Chem. Res. Toxicol. 2006, 19, 908-913.
138. Ding, S.; Jia, L.; Durandin, A. Absolute configurations of spiroiminodihy- dantoin and allantoin stereoisomers: comparison of computed and measured electronic circular dichroism spectra. Chem. Res. Toxicol. 2009, 22, 1189-1193.
139. Giorgio, E.; Roje, M.; Tanaka, K. Determination of the absolute configuration of flexible molecules by ab initio ord calculations: a case study with cytoxazones and isocytoxazones. J. Org. Chem. 2005, 70, 6557-6563.
140. Harada, N.; Nakanishi, K. Circular Dichroic Spectroscopy - Exciton Coupling in Organic Chemistry. University Science Books, Mill Valley, CA 1983.
141. Stephens, P. J.; Harada, N. ECD Cotton Effect Approximated by the Gaussian Curve and Other Methods Chirality 2010, 22, 229-233.
142. Bodensieck, A.; Fabian, W. M. F.; Kunert, O.; Belaj, F.; Jahangir, S.; Schühly, W.; Bauer, R. Absolute configuration of eremophilane sesquiterpe- nes from Petasites hybridus: Comparison of experimental and calculated circular dichroism spectra. Chirality 2009, 22, 308-319.
143. Grimme, S.; Waletzke, M. A combination of Kohn-Sham density functional theory and multi-reference configuration interaction methods. J. Chem. Phys. 1999, 111, 5645-5655.
144. Stephens, P. J.; Pan, J.-J.; Devlin, F. J.; Urbanová, M.; Julínek, O.; Hájí ek, J. Determination of the absolute configurations of natural products via density functional theory calculations of vibrational circular dichroism, electronic circular dichroism, and optical rotation: the iso-schizozygane alkaloids isoschizogaline and isoschizogamine. Chirality 2008, 20, 454-470.
145. Alonso-Gómez, J. L.; Petrovic, A. G.; Harada, N.; Rivera-Fuentes, P.; Berova, N.; Diederich, F. Chiral induction from allenes into twisted l,l,4,4- tetracyanobuta-1,3- dienes (TCBDs): Conformational assignment by circular dichroism spectroscopy. Chem. Eur. J. 2009, 15, 8396-8400.
146. Nafie, L. A. Dual polarization modulation: a real-time, spectral-multiplex separation of circular dichroism from linear birefringence spectral intensities. Appl. Spectrosc. 2000, 54, 1634-1645.
147. Nafie, L. A.; Buijs, H.; Rilling, A.; Cao, X.; Dukor, R. K. Dual source Fourier transform polarization modulation spectroscopy: an improved method for the measurement of circular and linear dichroism. Appl. Spectrosc. 2004, 58, 647-654.
148. Guo, C.; Shah, R. D.; Dukor, R. K.; Freedman, T. B.; Cao, X.; Nafie, L. A. Fourier transform vibrational circular dichroism from 800 to 10,000 cm-1: Near-IR-VCD spectral standards for terpenes and related molecules. Vib. Spectrosc. 2006, 42, 254-272.
149. Stephens, P. J. Theory of vibrational circular dichroism. J. Phys. Chem. 1985, 89, 748-752.
150. Stephens, P. J. Gauge dependence of vibrational magnetic dipole transition moments and rotational strengths. J. Phys. Chem. 1987, 91, 1712-1715.
151. Buckingham, A. D.; Fowler, P. W.; Galwas, P. A. Velocity-Dependent property surfaces and the theory of vibrational circular dichroism. Chem. Phys. 1987, 112, 1-14.
152. Urbanova, M. Bioinspired interactions studied by vibrational circular dichoism. Chirality 2009, 21, e215-e230.
153. Stephens, P. J.; Devlin, F. J.; Pan, J. The determination of the absolute con- figurations of chiral molecules using vibrational circular dichroism (VCD) spectroscopy. Chirality 2008, 20, 643-663.
154. Nafie, L. A. Vibrational Circular Dichroism: A new tool for the solution- state determination of the structure and absolute configuration of chiral natural product molecules. Nat. Prod. Commun. 2008, 3, 451-166.
155. Taniguchi, T.; Miura, N.; Nishimura, S.; Monde, K. Vibrational circular dichroism: chiroptical analysis of biomolecules. Mol. Nutr. Food Res. 2004, 48, 246-254.
156. Freedman, T. B.; Cao, X.; Dukor, R.; Nafie, L. A. Absolute configuration determination of chiral molecules in the solution state using vibrational circular dichroism. Chirality 2003, 15, 743-758.
157. Minick, D. J.; Copley, R. C. B.; Szewczyk, J. R.; Rutkowske, R. D.; Miller, L. A. An investigation of the absolute configuration of the potent histamine H3 receptor antagonist GT-2331 using vibrational circular dichroism. Chirality 2007, 19, 731-740.
158. Yang, G.; Xu, Y. The effects of self-aggregation on the vibrational circular dichroism and optical rotation measurements of glycidol. Phys. Chem. Chem. Phys. 2008, 10, 6787-6795.
159. Cichewicz, R. H.; Clifford, L. J.; Lassen, P. R. Stereochemical determination and bioactivity assessment of (S)-(+)-curcuphenol dimers isolated from the marine sponge didiscus aceratus and synthesized through laccase biocataly- sis. Bioorg. Med. Chem. Lett. 2005, 13, 5600-5612.
160. Cerda-García-Rojas, C. M.; Catalán, C. A. N.; Muro, A. C.; Joseph-Nathan, P. Vibrational circular dichroism of africanane and lippifoliane sesquiterpe- nes from lippia integrifolia. J. Nat. Prod. 2008, 71, 967-971.
161. Cerda-García-Rojas, C. M.; García-Gutiérrez, H. A.; Hernández-Hernández, J. D.; Román-Marín, L. U.; Joseph-Nathan, P. Absolute configuration of ver- ticillane diterpenoids by vibrational circular dichroism. J. Nat. Prod. 2007, 70, 1167-1172.
162. Lassen, P. R.; Skytte, D. M.; Hemmingsen, L. Structure and absolute configuration of nyasol and hinokiresinol via synthesis and vibrational circular dichroism spectroscopy. J. Nat. Prod. 2005, 68, 1603-1609.