Entropic intermediates and hidden rate-limiting steps in seemingly concerted cycloadditions. Observation, prediction, and origin of an isotope effect on recrossing

Journal of the American Chemical Society

Volumn 134, Issue 4, 2012, Pages 1914-1917

  Gonzalez James, Ollie M ^a   Kwan, Eugene E ^a   Singleton, Daniel A ^a  

^a TEXAS A AND M UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBON-CARBON BOND; CYCLOADDITION TRANSITION; CYCLOADDITIONS; DICHLOROKETENE; DIELS-ALDER REACTION; ENERGY SURFACE; ENTROPIC BARRIER; ISOTOPE EFFECT; KINETIC ISOTOPE EFFECTS; ORGANOCATALYTIC; RATE LIMITING; RATE-LIMITING STEPS; STATISTICAL MODELS; TRANSITION STATE;

BUTENES; CARRIER MOBILITY; ISOTOPES; REACTION INTERMEDIATES;

CYCLOADDITION;

ISOTOPE;

ARTICLE; CHEMICAL REACTION KINETICS; CYCLOADDITION; DIELS ALDER REACTION; ENTROPY; OBSERVATIONAL STUDY; PREDICTION;

ALKENES; CARBON ISOTOPES; CYCLIZATION; DICHLOROETHYLENES; ENTROPY; KETONES; KINETICS; MOLECULAR STRUCTURE; QUANTUM THEORY;

EID: 84856466877     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja208779k     Document Type: Article

References (22)

1. Eyring, H. J. Chem. Phys. 1934, 3, 107-115
2. Hirschfelder, J. O.; Wigner, E. J. Chem. Phys. 1939, 7, 616-628
3. Truhlar, D. G.; Garrett, B. C. Acc. Chem. Res. 1980, 13, 440-448
4. Sun, L.; Hase, W. L.; Song, K. J. Am. Chem. Soc. 2001, 123, 5753-5756
5. Mann, D. J.; Hase, W. L. J. Am. Chem. Soc. 2002, 124, 3208-3209
6. Kakhiani, K.; Lourderaj, U.; Hu, W.; Birney, D.; Hase, W. L. J. Phys. Chem. A 2009, 113, 4570
7. Pritchard, H. O. J. Phys. Chem. A 2005, 109, 1400-1404
8. Hayes, R. L.; Fattal, E.; Govind, N.; Carter, E. A. J. Am. Chem. Soc. 2001, 123, 641-657
9. Ussing, B. R.; Hang, C.; Singleton, D. A. J. Am. Chem. Soc. 2006, 128, 7594-7607
10. Wang, Z.; Hirschi, J. S.; Singleton, D. A. Angew. Chem., Int. Ed. 2009, 48, 9156-9159
11. Singleton, D. A.; Szymanski, M. J. J. Am. Chem. Soc. 1999, 121, 9455-9456
12. Gonzalez,-James, O. M.; Zhang, X.; Datta, A.; Hrovat, D. A.; Borden, W. T.; Singleton, D. A. J. Am. Chem. Soc. 2010, 132, 12548-12549
13. Kelly, K. K.; Hirschi, J. S.; Singleton, D. A. J. Am. Chem. Soc. 2009, 131, 8382-8383
14. Hase, W. L.; Song, K. H.; Gordon, M. S. Comp. Sci. Eng. 2003, 5, 36-44
15. The trajectory times are very long compared to ordinary cycloadditions. See: Xu, L.; Doubleday, C. E.; Houk, K. N. J. Am. Chem. Soc. 2010, 132, 3029-3037
16. Recent work has used "hidden" to describe prospective transition states that might arise if a reaction is changed. Kraka, E.; Cremer, D. Acc. Chem. Res. 2010, 43, 591-601
17. Gonzalez-Lafont, A.; Moreno, M.; Lluch, J. M. J. Am. Chem. Soc. 2004, 126, 13089-13094
18. Miller, W. H. J. Chem. Phys. 1976, 65, 2216-2223
19. Ahrendt, K. A.; Borths, C. J.; MacMillan, D. W. C. J. Am. Chem. Soc. 2000, 122, 4243-4244
20. Gordillo, R.; Houk, K. N. J. Am. Chem. Soc. 2006, 128, 3543-3553
21. Zheng, J.; Zhang, S.; Corchado, J. C.; Chuang, Y.-Y.; Coitino, E. L.; Ellingson, B. A.; Truhlar, D. G. GAUSSRATE, version 2009-A; University of Minnesota: Minneapolis, MN, 2010.
22. Zheng, J.; POLYRATE -version 2010; University of Minnesota: Minneapolis, MN, 2010.