CASSCF molecular orbital calculations reveal a purely pseudopericyclic mechanism for a [3,3] sigmatropic rearrangement

Journal of the American Chemical Society

Volumn 132, Issue 7, 2010, Pages 2196-2201

  Forte, Lila ^a   Lafortune, Marie C ^a   Bierzynski, Irena R ^a   Duncan, James A ^a  

^a LEWIS AND CLARK COLLEGE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVE SPACES; CARBONYL CARBON; CAS-SCF; COMPUTATIONAL STUDIES; KETENE MOIETY; LONE PAIR; MOLECULAR ORBITAL CALCULATIONS; SIGMATROPIC REARRANGEMENTS; TRANSITION STRUCTURES;

MOLECULAR ORBITALS;

KETENE DERIVATIVE; NITROGEN; PROPANE;

ARTICLE; CALCULATION; CHEMICAL STRUCTURE; GEOMETRY; ORBIT; REACTION ANALYSIS;

EID: 77749289370     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja906679g     Document Type: Article

References (30)

1. (a) Ross, J. A.; Seiders, R. P.; Lemal, D. M. J. Am. Chem. Soc. 1976, 98, 4325-4327.
2. (b) Birney, D. M.; Wagenseller, P. E. J. Am. Chem. Soc. 1994, 116, 6262-6270.
3. (c) Birney, D. M.; Ham, S.; Unruh, G. R. J. Am. Chem. Soc. 1997, 119, 4509-4517.
4. (d) Ji, H.; Xu, X.; Ham, S.; Hammad, L. A.; Birney, D. M. J. Am. Chem. Soc. 2009, 131, 528-537, and references therein.
5. (a) Duncan, J. A.; Calkins, D. E. G.; Chavarha, M. J. Am. Chem. Soc. 2008, 130, 6740-6748.
6. (b) Rodríguez-Otero, J.; Cabaleiro-Lago, E.; García- López, R.; Peña-Gallego, A.; Hermida-Ramón, J. Chem.-Eur. J. 2005, 11, 5966-5974.
7. (c) Rodríguez-Otero, J.; Cabaleiro-Lago, E.; Varela-Varela, S.; Peña-Gallego, A.; Hermida-Ramón, J. Org. Chem. 2005, 70, 3921-3928.
8. (d) Birney, D. J. Org. Chem. 1996, 61, 243-251.
9. (e) Rodríguez-Otero, J.; Cabaleiro-Lago, E. Chem. -Eur. J. 2003, 9, 1837-1843.
10. (f) Matito, E.; Poater, J.; Duran, M.; Solà, M. ChemPhysChem 2006, 7, 111-113.
11. (g) Chamorro, E. E.; Notario, R. J. Phys. Chem. A 2004, 108, 4099&-4104.
12. (h) López, C. S.; Faza, O. N.; Cossio, F. P.; York, D. M.; de Lera, A. R. Chem.-Eur. J. 2005, 11, 1734-1738.
13. Duncan, J. A.; Azar, J. K.; Beathe, J. C.; Kennedy, S. R.; Wulf, C. M. J. Am. Chem. Soc. 1999, 121, 12029-12034.
14. Hrovat, D. A.; Duncan, J. A.; Borden, W. T. J. Am. Chem. Soc. 1999, 127, 169-175.
15. Duncan, J. A.; Spong, M. C. J. Org. Chem. 2000, 65, 5720-5727.
16. Duncan, J. A.; Calkins, D. E. G.; Forte, L.; Delaney, F. E.; Lafortune, M. C.; Chavarha, M. Unpublished results.
17. (a) Frisch, M. J.; et al. Gaussian 03, Revisions D.01 and E.01; Gaussian, Inc.: Wallingford, CT, 2004.
18. (b) Frisch, M. J.; et al. Gaussian 09, Revision A.0.1; Gaussian, Inc.: Wallingford, CT, 2009.
19. Improvements in Gaussian 09, over Gaussian 03, made it possible for these large active space CASSCF-level IRCs to be examined.
20. Bode, B. M.; Gorgon, M. S. J. Mol. Graphics Modell. 1998, 16, 133-138.
21. As depicted in Figure 2, orbitais n and q both show only a small orbital contribution at one carbon atom. However, this is just an artifact resulting from the contour level chosen to make their representations relatively consistent with the other orbitais shown in the figure.
22. 23→-24 was calculated to have an energy 8.31 kcal/ mol higher than the reported one.
23. (a) Cossío, F. P.; Arrieta, A.; Sierra, M. A. Acc. Chem. Res. 2008, 41, 925-936.
24. (b) Fu, N.; Tidwell, T. T. Tetrahedron 2008, 64, 10465-10496.
25. 15→16 is headed toward product 16 with rather comparable C4-C5 bond breaking and C2- N7 bond making. Thus it doesn't appear to be on a trajectory to a zwitterionic intermediate with relatively short C4-C5 and C2-N7 bonds, which might open to 16 via C4-C5 bond cleavage without a barrier.
26. Wiest, O.; Black, K. A.; Houk, K. N. J. Am. Chem. Soc. 1994, 116, 10336-10337.
27. 27→-28which we also consider to possess a certain amount of pseudopericyclic character.
28. 31→32as we were unsuccessful in locating the correct active space for reactant 31.
29. (a) Braisted, A. C.; Schultz, P. G. J. Am. Chem. Soc. 1994, 116, 2211-2212.
30. (b) Ulrich, H. D.; Mundorff, E.; Santarsiero, B. D.; Driggers, E. M.; Stevens, R. C.; Schultz, P. G. Nature 1997, 389, 271-275.