Isotope effects and the experimental transition state for a prototypical thermal ene reaction

Tetrahedron Letters

Volumn 40, Issue 51, 1999, Pages 8939-8943

  Singleton, Daniel A ^a   Hang, Chao ^a  

^a TEXAS A AND M UNIVERSITY   (United States)

Author keywords

Ene reactions; Isotope effects; Mechanism; Transition states

Indexed keywords

ALKYLBENZENE; CARBON 13; DEUTERIUM; MALEIC ANHYDRIDE;

ARTICLE; CHEMICAL BOND; CHEMICAL MODIFICATION; CHEMICAL STRUCTURE; EXPERIMENTATION; GEOMETRY; HEAT; MODEL; STEREOCHEMISTRY;

EID: 0033579583     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)01923-1     Document Type: Article

References (32)

1. Grdina, B.; Orfanopoulos, M.; Stephenson, L. M. J. Am. Chem. Soc. 1979, 101, 3111.
2. Seymour, C. A.; Greene, F. D. J. Org. Chem. 1982, 47, 5226.
3. Stephenson, L. M.; Speth, D. R. J. Org. Chem. 1979, 44, 4683.
4. Cheng, C.-C.; Seymour, C. A.; Petti, M. A.; Greene, F. D.; Blount, J. F. J. Org. Chem. 1984, 49, 2910.
5. Snider, B. B.; Ron, E. J. Am. Chem. Soc. 1985, 107, 8160.
6. Kwart, H.; Brechbiel, M. W. J. Org. Chem. 1982, 47, 3353.
7. (a) Loncharich, R. J.; Houk, K. N. J. Am. Chem. Soc. 1987, 109, 6947.
8. (b) Bachrach, S. M.; Jiang, S. J. Org. Chem. 1997, 62, 8319.
9. (c) Deng, Q.; Thomas, B. E.; Houk, K. N.; Dowd, P. J. Am. Chem. Soc. 1997, 119, 6902.
10. (d) Pranata, J. Int. J. Quantum Chem. 1997, 62, 509.
11. (e) Uchimaru, T.; Tsuzuki, S.; Tanabe, K.; Hayashi, Y. Bull. Chem. Soc. Jpn. 1990, 63, 2246.
12. (a) Yliniemelä, A.; Konschin, H.; Pietilä, L.-O.; Teleman, O. J. Mol. Struc. Theochem 1995, 334, 173.
13. (b) Yliniemelä, A.; Konschin, H.; Neagu, C.; Pajunen, A.; Hase, T.; Brunow, G.; Teleman, O. J. Am. Chem. Soc. 1995, 117, 5120.
14. (a) Beno, B. R.; Houk, K. N.; Singleton, D. A. J. Am. Chem. Soc. 1996, 118, 9984.
15. (b) Singleton, D. A.; Merrigan, S. R.; Liu, J.; Houk, K. N. J. Am. Chem. Soc. 1997, 119, 3385.
16. (c) DelMonte, A. J.; Haller, J.; Houk, K. N.; Sharpless, K. B.; Singleton, D. A.; Straßner, T.; Thomas, A. A. J. Am. Chem. Soc. 1997, 119, 9907.
17. (d) Keating, A. E.; Merrigan, S. R.; Singleton, D. A.; Houk, K. N. J. Am. Chem. Soc. 1999, 121, 3933.
18. Singleton, D. A.; Thomas, A. A. J. Am. Chem. Soc. 1995, 117, 9357.
19. Based on fractionation factors in Baddenbaum, W. E.; Shiner Jr., V. J. In Isotope Effects on Enzyme-Catalyzed Reactions; Cleland, W. W.; O'Leary, M. H.; Northrop, D. B., Eds.; University Park Press: Baltimore, 1977; Chapter 1.
20. Achmatowicz Jr., O.; Szymoniak, J. J. Org. Chem. 1980, 45, 4774.
21. (a) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. For reviews of density-functional methods see:
22. (b) Ziegler, T. Chem. Rev. 1991, 91, 651.
23. (c) Density Functional Methods in Chemistry; Labanowski, J.; Andzelm, J., Eds.; Springer: Berlin, 1991.
24. (d) Parr, R. G.; Yang, Y. Density-functional Theory of Atoms and Molecules; Oxford University Press: New York, 198 9.
25. Benn, F. R.; Dwyer, J. J. Chem. Soc., Perkin Trans. 2 1977, 533.
26. (a) Bigeleisen, J.; Mayer, M. G. J. Chem. Phys. 1947, 15, 261.
27. (b) Wolfsberg, M. Acc. Chem. Res. 1972, 5, 225. The calculations used the program QUIVER (Saunders, M.; Laidig, K. E.; Wolfsberg, M. J. Am. Chem. Soc. 1989, 111, 8989) with frequencies scaled by 0.9614.
28. (b) Wolfsberg, M. Acc. Chem. Res. 1972, 5, 225. The calculations used the program QUIVER (Saunders, M.; Laidig, K. E.; Wolfsberg, M. J. Am. Chem. Soc. 1989, 111, 8989) with frequencies scaled by 0.9614.
29. Bell, R. P. The Tunnel Effect in Chemistry; Chapman and Hall: London, 1980; pp. 60-63.
30. Lu, D.-h.; Maurice, D.; Truhlar, D. G. J. Am. Chem. Soc. 1990, 112, 6206.
31. The isotope effects reported in Ref. 6 do not correspond to the raw data given. The observed increase in proportion of deuterium in recovered allylbenzene would be indicative of a normal and not an inverse isotope effect.
32. Nahm, S. H.; Cheng, H. N. J. Org. Chem. 1986, 51, 5093.