Quantum-chemical simulation of 1H NMR spectra. 2. Comparison of DFT-based procedures for computing proton-proton coupling constants in organic molecules

Journal of Organic Chemistry

Volumn 76, Issue 12, 2011, Pages 4818-4830

  Bally, Thomas ^a   Rablen, Paul R ^b  

^a UNIVERSITY OF FRIBOURG   (Switzerland)

^b SWARTHMORE COLLEGE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACCURATE PREDICTION; B3LYP/6-31G; BASIS FUNCTIONS; BASIS SETS; CHEMICAL SPACE; COMPUTATIONAL PROTOCOLS; CPU TIME; DENSITY FUNCTIONALS; FERMI CONTACT TERM; GAUSSIANS; H NMR SPECTRA; LINEAR SCALING; NUCLEAR COUPLING; ORGANIC MOLECULES; PROTON-PROTON COUPLING CONSTANTS; QUANTUM-CHEMICAL SIMULATIONS; RMS DEVIATIONS; ROOT-MEAN SQUARE DEVIATION; TEST SETS; TRAINING SETS;

CHEMICAL CONTAMINATION; COMPLEXATION; FORECASTING; NUCLEAR MAGNETIC RESONANCE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PROTONS; QUANTUM CHEMISTRY;

MOLECULES;

ORGANIC COMPOUND; PROTON;

ARTICLE; CHEMICAL STRUCTURE; DENSITY FUNCTIONAL THEORY; MOLECULAR INTERACTION; MOLECULE; PROTON NUCLEAR MAGNETIC RESONANCE; QUANTUM CHEMISTRY;

EID: 79958837486     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo200513q     Document Type: Article

References (52)

1. Günther, H., NMR Spectroscopy: Basic Principles, Concepts and Applications in Chemistry, 2 nd ed; John Wiley & Sons: New York, 1995
2. Bifulco, G.; Dambruoso, P.; Gomez-Paloma, L.; Riccio, R. Chem. Rev. 2007, 107, 3744
3. Helgaker, T.; Jaszuński, M.; Ruud, K. Chem. Rev. 1999, 99, 293
4. Bagno, A. Chem.-Eur. J. 2001, 7, 1652
5. Bagno, A.; Saielli, G. Theor. Chem. Acc. 2007, 117, 603
6. Krivdin, L. B. H. C. R. Ann. Rep. NMR Spectrosc. 2007, 61, 133
7. Helgaker, T.; Jaszuński, M.; Pecul, M. Prog. Nucl. Magn. Reson. Spectrosc. 2008, 53, 249
8. Kaupp, M.; Bühl, M.; Malkin, V. G., Eds.; Calculation of NMR and EPR Parameters; Wiley-VCH: Weinheim, 2004. See in particular Chapter 7 by Helgaker and Pecul on the calculation of spin-spin coupling constants (pp 101 ff.)
9. Bagno, A.; Rastrelli, F.; Saielli, G. Magn. Reson. Chem. 2008, 46, 518
10. Bifulco, G.; Bassarello, C.; Riccio, R.; Gomez-Paloma, L. Org. Lett. 2004, 6, 1025
11. Di Micco, S.; Chini, M. G.; Riccio, R.; Bifulco, G. Eur. J. Org. Chem. 2010, 1411 and references cited therein
12. Katritzky, A. R.; Akhmedov, N. G.; Doskocz, J.; Hall, C. D.; Akhmedova, R. G.; Majumder, S. Magn. Reson. Chem. 2007, 45, 5
13. Mendoza-Espinoza, J. A.; López-Vallejo, F.; Fragoso-Serrano, M.; Pereda-Miranda, R.; Cerda-García-Rojas, C. J. Nat. Prod. 2009, 72, 700
14. Merrick, J.; Moran, D.; Radom, L. J. Phys. Chem. A 2007, 111, 11683
15. Petrovic, A. G.; Navarro-Vázquez, A.; Alonso-Gómez, J. Curr. Org. Chem. 2010, 14, 1612 and references cited therein
16. Poza, J. J.; Jimenéz, C.; Rodriguez, J. Eur. J. Org. Chem. 2008, 3960
17. Smith, S. G.; Goodman, J. M. J. Am. Chem. Soc. 2010, 132, 12946 and references cited therein
18. Jain, R.; Bally, T.; Rablen, P. R. J. Org. Chem. 2009, 74, 4017
19. Karplus, M. J. Am. Chem. Soc. 1963, 85, 2870
20. Houseknecht, J. B.; Altona, C.; Hadad, C. M.; Lowary, T. L. J. Org. Chem. 2002, 67, 4647 and references cited therein
21. It is this perturbation which is responsible for the transmission of the information on the magnetic moment of a given nucleus to the other nuclei and thus leads to the coupling of the nuclear spins.
22. Lantto, P.; Vaara, J.; Helgaker, T. J. Chem. Phys. 2002, 117, 5998
23. Lutnæs, O. B.; Helgaker, T.; Jaszuński, M. Mol. Phys. 2010, 108, 2579
24. Helgaker, T.; Lutnæs, O. B.; Jaszuński, M. J. Chem. Theor. Comput. 2007, 3, 86
25. Jensen, F. J. Chem. Theor. Comput. 2006, 2, 1360
26. Helgaker, T.; Jaszuński, M.; Ruud, K.; Górska, A. Theor. Chem. Acc. 1998, 99, 175
27. Lutnæs, O. B.; Ruden, T. A.; Helgaker, T. Magn. Reson. Chem. 2004, 42, S117
28. Deng, W.; Cheeseman, J. R.; Frisch, M. J. J. Chem. Theory Comput. 2006, 2, 1028
29. Frisch, M. J. et al. Gaussian09, Revision A.02; Gaussian, Inc.: Wallingford, CT, 2009, (full reference is given in the Supporting Information).
30. Krivdin, L. B. Magn. Reson. Chem. 2004, 42, S168 and references cited therein
31. Ruden, T. A.; Lutnæs, O. B.; Helgaker, T.; Ruud, K. J. Chem. Phys. 2003, 118, 9572
32. Yachmenev, A.; Yurchenko, S. N.; Paidarova, I.; Jensen, P.; Thiel, W.; Sauer, S. P. A. J. Chem. Phys. 2010, 132, 114305 and references cited therein
33. Ruden, T.; Helgaker, T.; Jaszuński, M. Chem. Phys. 2004, 296, 53
34. We are perfectly aware of the fact that many molecules that practicing organic chemists face every day show some conformational flexibility. To properly account for this requires accurate relative free energies of different conformations, which constitutes a compounding factor that we wanted to exclude from our present analysis.
35. Jackman, L. M.; Sternhell, S., Applications of Nuclear Magnetic Resonance Spectroscopy in Organic Chemistry, 2 nd ed.; Pergamon Press: New York, 1969
36. Crews, P.; Rodriguez, J.; Jaspars, M. Organic Structure Analysis; Oxford University Press: New York, 1998.
37. Gordon, A. J.; Ford, R. A., The Chemist's Companion: A Handbook of Practical Data, Techniques, and References. Wiley: New York, 1972
38. See, e.g., http://cccbdb.nist.gov/vibnotes.asp (accessed 1/25/2011).
39. Ochsenfeld, C.; Kussmann, F.; Koziol, F. Angew. Chem., Int. Ed. 2004, 43, 4485
40. This situation differs from that for chemical shifts, where a nonzero intercept reflects the fact that a chemical shift always represents a difference in magnetic shielding relative to some standard. Coupling constants, on the other hand, are absolute quantities, not referenced to a standard.
41. Wiitala, K. W.; Hoye, T. R.; Cramer, C. J. J. Chem. Theor. Comput. 2006, 2, 1085 In Gaussian, the WP04 functional is invoked by specifying the BLYP keyword and adding iop (3/76 = 1000001189, 3/77 = 0961409999, 3/78 = 0000109999) to the keyword line
42. Bagno, A.; Rastrelli, F.; Saielli, G. Chem.-Eur. J. 2006, 12, 5514
43. Other workers have also based predictions of proton coupling constants on calcualted FC terms alone, albeit with special basis set, decontracted and augmented on H-atoms: Diéz, E.; Casanueva, J.; San Fanian, J.; Esteban, A. L.; Galache, M. P.; Barone, V.; Peralta, J. E.; Contreras, R. H. Mol. Phys. 2005, 103, 1307
44. Zhao, Y.; Truhlar, D. G. Acc. Chem. Res. 2007, 41, 157
45. Schwabe, T.; Grimme, S. Acc. Chem. Res. 2008, 41, 569
46. Indeed, it has been established that for C-H coupling constants, it is at least sometimes important to include terms other than the Fermi contact term: Bagno, A.; Rastrelli, F.; Saielli, G. J. Phys. Chem. A. 2003, 107, 9964-9973
47. We also investigated B3LYP/6-311G(d,p)u+1s and B3LYP/cc-pVTZ u+1s in this manner; full details appear in the Supporting Information
48. 1,2,3-Butatriene has both a cis and a trans coupling, but the two are extremely similar, and only an averaged value is available from experiment.
49. Anet, F. A.; Schlenk, G. E. J. Am. Chem. Soc. 1971, 93, 556
50. Naor, R.; Luz, Z. J. Chem. Phys. 1982, 76, 5662
51. The group of Tantillo at UC Davies has set up a website called "Chemical Shift Repository" (CHESHIRE) where these scripts, including updated versions, are posted. See: http://cheshirenmr.info.
52. http://mestrelab.com/ (accessed 2/5/2011).