Secondary orbital effect in the electrocyclic ring closure of 7-azahepta-1,2,4,6-tetraene - A CASSCF molecular orbital study

Journal of the American Chemical Society

Volumn 130, Issue 21, 2008, Pages 6740-6748

  Duncan, James A ^a   Calkins, David E G ^a   Chavarha, Mariya ^a  

^a LEWIS AND CLARK COLLEGE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL BONDS; DENSITY FUNCTIONAL THEORY; MOLECULAR ORBITALS;

ELECTROCYCLIC RING CLOSURE; SECONDARY ORBITAL EFFECT;

ORGANIC COMPOUNDS;

7 AZAHEPTA 1,2,4,6 TETRAENE 3; POLYAMINE;

ARTICLE; CYCLIZATION; DENSITY FUNCTIONAL THEORY; ELECTROLYSIS; MATHEMATICAL COMPUTING; RING CLOSING METATHESIS;

EID: 44449088460     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja074402j     Document Type: Article

References (36)

1. Woodward, R. B.; Hoffmann, R. J. Am. Chem. Soc. 1965, 87, 395-397.
2. Wang, L. Chem. Eng. News 2006, 84, 49-50.
3. de Lera, A. R.; Alvarez, R.; Lecea, B.; Torrado, A.; Cissío, F. P. Angew. Chem., Int. Ed. 2001, 40, 557-561.
4. (a) Ross, J. A.; Seiders, R. P.; Lemal, D. M. J. Am. Chem. Soc. 1976, 98, 4325-4327.
5. (b) Birney, D. M.; Wagenseller, P. E. J. Am. Chem. Soc. 1994, 116, 6262-6270.
6. (c) Birney, D. M. J. Org. Chem. 1996, 61, 243-251.
7. (d) Birney, D. M.; Ham, S.; Unruh, G. R. J. Am. Chem. Soc. 1997, 119, 4509-4517.
8. Rodríguez-Otero, J.; Cabaleiro-Lago, E. Angew. Chem., Int. Ed. 2002, 41, 1147-1150.
9. 5 it was demonstrated that geometric and energetic results, as well as activation energies, were virtually identical to results obtained with the 6-31+G* basis set.
10. de Lera, A. R.; Cossío, F. P. Angew. Chem., Int. Ed. 2002, 41, 1150-1152.
11. Rodríguez-Otero, J.; Cabaleiro-Lago, E. Chem. Eur. J. 2003, 9, 1837-1843.
12. Chamorro, E. E.; Notario, R. J. Phys. Chem. A 2004, 108, 4099-4104.
13. Matito, E.; Solà, M.; Duran, M.; Poater, J. J. Phys. Chem. B 2005, 109, 7591-7593.
14. (a) Chamorro, E. E.; Notario, R. J. Phys. Chem. B 2005, 109, 7594-7595.
15. Also see: Matito, E.; Poater, J.; Duran, M.; Solà, M. ChemPhysChem 2006, 7, 111-113.
16. López, C. S.; Faza, O. N.; Cossío, F. P.; York, D. M.; de Lera, A. R. Chem. Eur. J. 2005, 11, 1734-1738.
17. (a) Duncan, J. A.; Azar, J. K.; Beathe, J. C.; Kennedy, S. R.; Wulf, C. M. J. Am. Chem. Soc. 1999, 121, 12029-12034.
18. (b) Duncan, J. A.; Hendricks, R. T.; Kwong, K. S. J. Am. Chem. Soc. 1990, 112, 8433-8442.
19. (c) Duncan, J. A.; Spong, M. C. J. Phys. Org. Chem. 2005, 18, 462-467.
20. The 5 → 6 rearrangement has also been studied extensively at the RHF level: Evanseck, J. D.; Thomas, B. E., IV; Spellmeyer, D. C.; Houk, K. N. J. Org. Chem. 1999, 60, 7134-7141.
21. The 9 → 11 and 10 → 11 rearrangements have also been studied extensively at the B3LYP level with similar results: Walker, M. J.; Hietbrink, B. N.; Thomas, B. E., IV; Nakamura, K; Kallel, E. A.; Houk, K. N. J. Org. Chem. 2001, 121, 6669-6672.
22. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
23. (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789.
24. (a) Frisch, M. J.; Gaussian 98, revision A.7; Gaussian, Inc.: Pittsburgh, PA, 1998.
25. (b) Frisch, M. J.; Gaussian 03, revision D.01; Gaussian, Inc.: Wallingford, CT, 2004..
26. Karlström, G.; Lindh, R.; Malmqvist, P.-Å.; Roos, B. O.; Ryde, U.; Veryazov, V.; Widmark, P.-O.; Cossi, M.; Schimmelpfennig, B.; Neogrady, P.; Seijo, L. Comp. Mater. Sci. 2003, 28, 222-239.
27. Bode, B. M.; Gorgon, M. S. J. Mol. Graphics Modell. 1998, 16, 113-138.
28. Woodward, R. B.; Hoffmann, R. The Conservation of Orbital Symmetry; Academic Press: New York, 1970.
29. 3→4-B3LYP in Figure 3.
30. 10→11 of 17.8 kcal/mol (as opposed to 17.2 kcal/mol based on activation enthalpies) and a B3LYP one of 17.0 kcal/mol (as opposed to 16.7 kcal/mol based on activation enthalpies).
31. In a few cases, some of the tiniest AO contributions had to be omitted in the transition structure bonding and antibonding MOs of Figures 5-7. All of the actual MOs can be found in Supporting Information.
32. Cabaleiro-Lago, E. M.; Rodríguez-Otero, J.; García- López, R. M.; Peña-Gallego, A.; Hermida-Ramón, J. M. Chem. Eur. J. 2005, 11, 5966-5974.
33. a] one.
34. 2 group in 5 is predicted to rotate clockwise in model D of Figure 1 as it does in model A, may make the process best described as disrotatory.
35. 3→4 in the 10 → 11 the 3 → 4 rearrangements to be.
36. While this manuscript was in revision, we became aware of a paper by Professor Shogo Sakai (Theor. Chem. Acc. DOI 10.1007/s00214-007-0312-8). He performed similar calculations on the electrocyclizations of 3, 5, and 12 and reached similar conclusions, though he used a CiLC-IRC approach and multiconfigurational second-order Møller-Plesset perturbation theory (MRMP), instead of CASPT2, to incorporate configuration interaction.