How do ring currents affect 1H NMR chemical shifts?

Organic Letters

Volumn 5, Issue 5, 2003, Pages 605-608

  Wannere, Chaitanya S ^a   Schleyer, Paul Von Ragué ^a  

^a UNIVERSITY OF GEORGIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

1,3 BUTADIENE DERIVATIVE; ACETYLENE; ANTHRACENE; BENZENE; CYCLOPROPANE; ETHANE; ETHYLENE; HYDROGEN; NAPHTHALENE; PROPYLENE; PROTON; TOLUENE; VINYL DERIVATIVE;

AB INITIO CALCULATION; ANISOTROPY; ARTICLE; CROSS LINKING; ELECTRON; HYDROGEN BOND; MOLECULE; PROTON NUCLEAR MAGNETIC RESONANCE; STRUCTURE ANALYSIS;

EID: 0042048202     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol027327k     Document Type: Article

References (47)

1. (a) Pople, J. A. J. Chem. Phys. 1956, 24, 1111.
2. (b) Pople, J. A. Mol. Phys. 1958, 1, 175.
3. (c) Haigh, C. W.; Mallion, R. B. Prog. Nucl. Magn. Reson. Spectrosc. 1980, 13, 303.
4. (d) Lazzeretti, P. Prog. Nucl. Magn. Reson. Spectrosc. 2000, 36, 1.
5. (e) Gomes, J. A. N. F.; Mallion, R. B. Chem. Rev. 2001, 101, 1349.
6. (a) Pople, J. A.; Schneider, W. G.; Bernstein, H. J. High-Resolution Nuclear Magnetic Resonance; McGraw-Hill: New York, 1959.
7. (b) Günther, H. NMR Spectroscopy; Wiley: New York, 1998; p 85.
8. (c) Silverstein, R. M.; Bassler, G. C.; Morill, T. C. Spectrometric Identification of Organic Compounds; Wiley and Sons: New York, 1991.
9. (a) Pauling, L. J. Chem. Phys. 1936, 4, 673.
10. (b) Lonsdale, K. Proc. R. Soc. London, 1937, 159, 149.
11. (c) London, F. J. Phys. Radium 1937, 8, 397.
12. (d) London, F. J. Chem. Phys. 1937, 5, 837.
13. (a) Musher, J. I. J. Chem. Phys. 1967, 47, 1219.
14. (b) Musher, J. I. Adv. Magn. Reson. 1966, 2, 177.
15. (c) Musher, J. I. J. Chem. Phys. 1965, 43, 4041.
16. Gaidis, J. M.; West, R. J. J. Chem. Phys. 1967, 46, 1218.
17. (a) Blustin, P. H. Chem. Phys. Lett. 1979, 64, 507.
18. (b) Blustin, P. H. Mol. Phys. 1978, 36, 1441.
19. (c) Blustin, P. H. Mol. Phys. 1980, 39, 565.
20. Fleischer, U.; Kutzelnigg, W.; Lazzeretti, P.; Mühlenkamp, V. J. Am. Chem. Soc. 1994, 116, 5298.
21. McConnell, H. M. J. Chem. Phys. 1957, 27, 1.
22. Johnson, C. E.; Bovey, F. A. J. Chem. Phys. 1958, 29, 1012
23. (a) Schleyer, P. v. R.; Manoharan, M.; Wang, Z. X.; Kiran, B.; Jiao, H.; Puchta, R.; Hommes, N. J. R. v. E. Org. Lett. 2001, 3, 2465.
24. (b) Klod, S.; Kleinpeter, E. J. Chem. Soc., Perkin Trans. 2 2001, 1893.
25. (c) Martin, N.; Brown, J. D.; Nance, K. H.; Schaefer, H. F., III; Schleyer, P. v. R.; Wang, Z.-X.; Woodcock, H. L. Org. Lett. 2001, 3, 3823.
26. (d) Klod, S.; Andreas, K.; Kleinpeter, E. J. Chem. Soc., Perkin Trans. 2 2002, 1506.
27. (e) Martin, N. H.; Allen, N. W., III; Minga, E. K.; Ingrassia, S. T.; Brown, J. D. J. Am. Chem. Soc. 1998, 120, 11510.
28. (a) Kutzelnigg, W. Isr. J. Chem. 1980, 19, 193.
29. (b) Schindler, M.; Kutzelnigg, W. J. Chem. Phys. 1982, 76, 1919.
30. (c) Schindler, M.; Kutzelnigg, W. J. Am. Chem. Soc. 1983, 105, 1360.
31. (d) Kutzelnigg, W. THEOCHEM 1989, 202, 11.
32. (e) Kutzelnigg, W.; Fleischer, U.; Schindler, M. In NMR: Basic Principles of Progress; Springer: Berlin, 1990; Vol. 23, p 165.
33. Absolute proton shieldings were computed using the IGLO method and the Pipek-Mezey localization procedure as implemented in the deMon NMR program (Malkin, V. G.; Malkina, O. L.; Casida, M. E.; Salahub, D. R. J. Am. Chem. Soc. 1994, 116, 5898) at the PW91/IGLO-III//B3LYP/6-311+G** level. The chemical shifts, in ppm, are evaluated relative to TMS (the proton chemical shieldings were converted to chemical shifts as the difference from the proton shieldings of TMS, 31.3 ppm). Geometry optimizations, in most stable conformations, were done at the B3LYP/6-311+G** level using Gaussian 98 (Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, revision A.5; Gaussian, Inc.: Pittsburgh, PA, 1998).
34. Absolute proton shieldings were computed using the IGLO method and the Pipek-Mezey localization procedure as implemented in the deMon NMR program (Malkin, V. G.; Malkina, O. L.; Casida, M. E.; Salahub, D. R. J. Am. Chem. Soc. 1994, 116, 5898) at the PW91/IGLO-III//B3LYP/6-311+G** level. The chemical shifts, in ppm, are evaluated relative to TMS (the proton chemical shieldings were converted to chemical shifts as the difference from the proton shieldings of TMS, 31.3 ppm). Geometry optimizations, in most stable conformations, were done at the B3LYP/6-311+G** level using Gaussian 98 (Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, revision A.5; Gaussian, Inc.: Pittsburgh, PA, 1998).
35. (a) Memory, J. D.; Wilson, N. K. NMR of Aromatic Compounds; Wiley and Sons: New York, 1982.
36. (b) Cram, D. J.; Tanner, M. E.; Thomas, R. Angew. Chem., Int. Ed. Engl. 1991, 30, 1024.
37. (c) Trahanovsky, W. S.; Fischer, D. R. J. Am. Chem. Soc. 1990, 112, 4971.
38. For a comparison of CC(Π) shielding grids of benzene, acetylene, cyclobutadiene, and trans-dihydropyrene, see Supporting Information.
39. Haigh, C. W.; Mallion, R. B. J. Chem. Phys. 1982, 76, 4063.
40. (a) Pople, J. A.; Untch, K. G. J. Am. Chem. Soc. 1966, 88, 4811.
41. (b) We will analyze large antiaromatic systems in a separate paper.
42. Bally, T.; Masamune, S. Tetrahedron 1980, 36, 343.
43. Schleyer, P. v. R.; Manoharan, M.; Jiao, H.; Stahl, F. Org. Lett. 2001, 3, 3643.
44. (a) Jiao, H.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1996, 35, 2383.
45. (b) Baldridge, K. K.; Siegel, J. S. Angew. Chem., Int. Ed. Engl. 1997, 36, 745.
46. (c) Choi, C. H.; Kertesz, M. J. Chem. Phys. 1998, 108, 6681.
47. (d) Wannere, C. S.; Schleyer, P. v. R. Org. Lett. Submitted.