Calculations on tunneling in the reactions of noradamantyl carbenes

Journal of the American Chemical Society

Volumn 135, Issue 46, 2013, Pages 17274-17277

  Kozuch, Sebastian ^a   Zhang, Xue ^a   Hrovat, David A ^a   Borden, Weston Thatcher ^a  

^a UNIVERSITY OF NORTH TEXAS   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBENES; CRYOGENIC TEMPERATURES; HYDROGEN MIGRATION; ORDERS OF MAGNITUDE; RING EXPANSION; SMALL-CURVATURE TUNNELING;

CHEMISTRY; SYNTHESIS (CHEMICAL);

RATE CONSTANTS;

CARBENE; HYDROGEN; NITROGEN; NORADAMANTYLCHLOROCARBENE; UNCLASSIFIED DRUG;

ARTICLE; CALCULATION; CHEMICAL ANALYSIS; CHEMICAL MODIFICATION; CHEMICAL REACTION; COLD;

EID: 84888372066     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja409176u     Document Type: Article

References (33)

1. Sheridan, R. S. In Reviews of Reactive Intermediate Chemistry; Platz, M. S., Moss, R. A., Jones, M., Jr., Eds.; John Wiley & Sons: New York, 2007; pp 415-463.
2. Ley, D.; Gerbig, D.; Schreiner, P. Org. Biomol. Chem. 2012, 10, 3781
3. Whitman, D. W.; Carpenter, B. K. J. Am. Chem. Soc. 1980, 102, 4272
4. Whitman, D. W.; Carpenter, B. K. J. Am. Chem. Soc. 1982, 104, 6473
5. Carpenter, B. K. J. Am. Chem. Soc. 1983, 105, 1700
6. Huang, M. J.; Wolfsberg, M. J. Am. Chem. Soc. 1984, 106, 4039
7. Dewar, M. J. S.; Merz, K. M., Jr.; Stewart, J. J. P. J. Am. Chem. Soc. 1984, 106, 4040
8. Lefebvre, R.; Moiseyev, N. J. Am. Chem. Soc. 1990, 112, 5052
9. Redington, R. L. J. Chem. Phys. 1998, 109, 10781
10. Spectroscopic evidence for tunneling in the automerization of cyclobutadiene was subsequently obtained in experiments carried out by Michl and co-workers. This research has been reviewed: Arnold, B. R.; Michl, J. In Spectroscopy of Carbenes and Biradicals; Platz, M. S., Ed.; Plenum Press: New York, 1990; p 1.
11. Zuev, P. S.; Sheridan, R. S.; Albu, T. V.; Truhlar, D. G.; Hrovat, D. A.; Borden, W. T. Science 2003, 299, 867
12. Zhang, X.; Hrovat, D. A.; Borden, W. T. Org. Lett. 2010, 12, 2798
13. Datta, A.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 2008, 130, 6684
14. Gonzalez-James, O. M.; Zhang, X.; Datta, A.; Hrovat, D. A.; Borden, W. T.; Singleton, D. A. J. Am. Chem. Soc. 2010, 132, 12548
15. Bergman cyclization of cyclodec-3-ene-1,5-diyne: Greer, E. M.; Cosgriff, C. V.; Doubleday, C. J. Am. Chem. Soc. 2013, 135, 10194
16. Ertelt, M.; Hrovat, D. A.; Borden, W. T.; Sander, W. Ring opening of 1H-bicyclo[3.1.0]hexa-3,5-diene-2-one at low temperatures: Chem.-Eur. J. 2013, submitted
17. Moss, R. A.; Sauers, R. R.; Sheridan, R. S.; Tian, J.; Zuev, P. S. J. Am. Chem. Soc. 2004, 126, 10196
18. Tunneling rates are expected to decrease exponentially with the barrier width times the square root of the effective tunneling mass. Bell, R. P., The Tunnel Effect in Chemistry; Chapman and Hall: New York, 1980.
19. Becke, A. D. J. Chem. Phys. 1993, 98, 5648
20. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 78
21. Miehlich, B.; Savin, A.; Stoll, H.; Preuss, H. Chem. Phys. Lett. 1989, 157, 200
22. Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257
23. Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213
24. Truhlar, D. G.; Garrett, B. C. Annu. Rev. Phys. Chem. 1984, 35, 159
25. Fernandez-Ramos, A.; Ellingson, B. A.; Garrett, B. C.; Truhlar, D. G. In Reviews in Computational Chemistry; Lipkowitz, K. B.; Cundari, T. R., Eds.; John Wiley & Sons, Inc.: New York, 2007; pp 125-232.
26. B to 3d
27. Corchado, J. C.; POLYRATE 2010-A; University of Minnesota, Minneapolis, MN, 2010.
28. Corchado, J. C.; GAUSSRATE 2009-A; University of Minnesota, Minneapolis, MN, 2010.
29. Frisch, M. J.;; Gaussian 09, Revision B01; Gaussian, Inc., Wallingford, CT, 2009.
30. See, for example: Jones, M., Jr.; Moss, R. A. In Reactive Intermediate Chemistry; Moss, R. A.; Platz, M. S.; Jones, M., Jr., Eds.; John Wiley & Sons: New York, 2004; pp 273-328.
31. Tae, E. L.; Ventre, C.; Zhu, Z.; Likhotvorik, I.; Ford, F.; Tippmann, E.; Platz, M. S. J. Phys. Chem. A 2001, 105, 10146
32. Previous calculations on the two possible modes of ring expansion of 1a have found similar energy differences between the two products, 2a and 4a, formed and between the two TSs leading to them: Tae, E. L.; Ventre, C.; Zhu, Z.; Likhotvorik, I.; Ford, F.; Tippmann, E.; Platz, M. S. J. Phys. Chem. A 2001, 105, 10146
33. Schreiner and co-workers reported the results of calculations on the ring expansion of cyclopropylcarbene and on the 1,2-hydrogen shift in cyclopropylmethylcarbene. Unfortunately, they did not report the results of calculations on the ring expansion of cyclopropylmethylcarbene: Gerbig, D.; Ley, D.; Schreiner, P. Org. Lett. 2011, 13, 3526