σ-antiaromaticity in cyclobutane, cubane, and other molecules with saturated four-membered rings

Organic Letters

Volumn 5, Issue 1, 2003, Pages 23-26

  Moran, Damian ^a,b   Manoharan, Mariappan ^a   Heine, Thomas ^c   Schleyer, Paul Von Ragué ^a,b  

^a UNIVERSITY OF GEORGIA   (United States)

^b UNIVERSITY OF ERLANGEN NUREMBERG   (Germany)

^c DRESDEN UNIVERSITY OF TECHNOLOGY   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC COMPOUND; CARBON; CUBANE DERIVATIVE; CYCLOBUTANE; CYCLOPROPANE; HYDROCARBON;

ARTICLE; CHEMICAL BOND; CHEMICAL STRUCTURE; PROTON NUCLEAR MAGNETIC RESONANCE;

EID: 0012489685     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol027159w     Document Type: Article

References (27)

1. Minkin, V. I.; Glukhovtsev, M. N.; Simkin, B. Y. J. Mol. Struct. (THEOCHEM) 1988, 181, 93.
2. Dewar, M. J. S. J. Am. Chem. Soc. 1984, 106, 669.
3. Cremer, D.; Gauss, J. J. Am. Chem. Soc. 1986, 108, 7467.
4. Exner, K.; Schleyer, P. v. R. J. Phys. Chem. A 2001, 105, 3407.
5. Jackman, L. M.; Sternhell, S. Application of Nuclear Magnetic Resonance Spectroscopy in Organic Chemistry, 2nd ed.; Pergamon Press: Braunschweig, Germany, 1969.
6. Dauben, H. J.; Wilson, J. D.; Laity, J. L. In Nonbenzenoid Aromatics; Snyder, J. P., Ed.; Academic Press: New York, 1971.
7. Schleyer, P. v. R.; Puhlhofer, F. Org. Lett. 2002, 4, 2873.
8. Baeyer, A. Chem. Ber. 1885, 18, 2269.
9. Zhoa, M.; Gimarc, B. M. Inorg. Chem. 1996, 35, 5378.
10. Greenberg, A.; Liebman, J. F. Strained Organic Molecules; Academic Press: New York, 1978.
11. 4h cyclobutane.
12. Hoffmann, R.; Davidson, R. B. J. Am. Chem. Soc. 1971, 93, 5699.
13. Ahlrichs, R.; Brode, S.; Ehrhardt, C. J. Am. Chem. Soc. 1985, 107, 7260.
14. Sauers, R. R. Tetrahedron 1998, 54, 337.
15. Bettinger, H. F.; Pak, C. H.; Xie, Y. M.; Schleyer, P. v. R.; Schaefer, H. F. J. Chem. Soc., Perkin Trans. 2 1999, 2377.
16. 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.
17. 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.
18. Schleyer, P. v. R.; Maerker, C.; Dransfeld, A.; Jiao, H. J.; Hommes, N. J. r. V. E. J. Am. Chem. Soc. 1996, 118, 6317.
19. Schleyer, P. v. R.; Jiao, H.; Hommes, N. J. R. v. E.; Malkin, V. G.; Malkina, O. L. J. Am. Chem. Soc. 1997, 119, 12669.
20. Malkin, V. G.; Malkina, O. L.; Eriksson, L. A.; Salahub, D. R. J. Am. Chem. Soc. 1994, 116, 5898.
21. NICS points close to ethane also are deshielded, but to a much smaller extent. At the cyclopropane (0.871 Å) and cyclobutane (1.101 Å) carbon to ring center distances from the ethane C-C bond, the shielding is only -2.3 ppm and -0.2 ppm, respectively.
22. Heine, T.; Schleyer, P. v. R.; Corminboeuf, C.; Seifert, G.; Reviakine, R.; Weber, J. Jr. Am. Chem. Soc. 2002, submitted. For a related method, see: Corminboeuf, C.; Heine, T.; Weber, J. Phys. Chem. Chem. Phys. 2002, accepted. MO-NICS analysis gives the contributions of all the single canonical MOs; their total is the shielding tensor. In the GIAO method, the MO contribution of the shielding tensor can be taken directly from the orbital-based formulation given by eqs 27 and 28 in: Schreckenbach, G.; Ziegler, T. J. Phys. Chem. 1995, 99, 606.
23. Heine, T.; Schleyer, P. v. R.; Corminboeuf, C.; Seifert, G.; Reviakine, R.; Weber, J. Jr. Am. Chem. Soc. 2002, submitted. For a related method, see: Corminboeuf, C.; Heine, T.; Weber, J. Phys. Chem. Chem. Phys. 2002, accepted. MO-NICS analysis gives the contributions of all the single canonical MOs; their total is the shielding tensor. In the GIAO method, the MO contribution of the shielding tensor can be taken directly from the orbital-based formulation given by eqs 27 and 28 in: Schreckenbach, G.; Ziegler, T. J. Phys. Chem. 1995, 99, 606.
24. Heine, T.; Schleyer, P. v. R.; Corminboeuf, C.; Seifert, G.; Reviakine, R.; Weber, J. Jr. Am. Chem. Soc. 2002, submitted. For a related method, see: Corminboeuf, C.; Heine, T.; Weber, J. Phys. Chem. Chem. Phys. 2002, accepted. MO-NICS analysis gives the contributions of all the single canonical MOs; their total is the shielding tensor. In the GIAO method, the MO contribution of the shielding tensor can be taken directly from the orbital-based formulation given by eqs 27 and 28 in: Schreckenbach, G.; Ziegler, T. J. Phys. Chem. 1995, 99, 606.
25. Walsh, A. D. J. Chem. Soc. 1953, 2260.
26. Hirsch, A.; Chen, Z.; Jiao, H. Angew. Chem., Int. Ed. 2001, 40, 2834.
27. Chen, K. H.; Allinger, N. L. J. Mol. Struct. (THEOCHEM) 2002, 581, 215.