Solvolysis of optically active 4-methylcyclohexylidenemethyl triflate: Evidence against a primary vinyl cation as an intermediate

Chemistry Letters

Volumn , Issue 8, 2001, Pages 806-807

  Fujita, Morifumi ^a   Yamamoto, Akiyo ^a   Sugimura, Takashi ^a   Okuyama, Tadashi ^a  

^a UNIVERSITY OF HYOGO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0035538673     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.2001.806     Document Type: Article

References (30)

1. P. J. Stang, Z. Rappoport, M. Hanack, and L. R. Subramanian, "Vinyl Cations," Academic Press, New York (1979).
2. "Dicoordinated Carbocations," ed. by Z. Rappoport and P. J. Stang, John Wiley & Sons, Chichester (1997).
3. S. G. Lias, J. E. Bartmess, J. F. Liebman, J. L. Holmes, R. D. Levin, and W. G. Mallard, J. Phys. Chem. Ref. Data, 17, 1 (1988).
4. Nuclear decay: S. Fornarini and M. Speranza, Tetrahedron Lett., 25, 869 (1984); J. Am. Chem. Soc., 111, 7402 (1989).
5. Nuclear decay: S. Fornarini and M. Speranza, Tetrahedron Lett., 25, 869 (1984); J. Am. Chem. Soc., 111, 7402 (1989).
6. Photochemical reactions: G. Lodder, in "Dicoordinated Carbocations," ed. by Z. Rappoport and P. J. Stang, John Wiley & Sons, Chichester (1997), Chap. 8.
7. In superacid: H. Hogeveen and C. F. Roobeek, Tetrahedron Lett., 1971, 3343.
8. In concentrated sulfuric acid: L. Lucchini and G. Modena, J. Am. Chem. Soc., 112, 6291 (1990).
9. M. Hanack, R. Märkl, and A. G. Martinez, Chem. Ber., 115, 772 (1982).
10. a) T. Okuyama and M. Ochiai, J. Am. Chem. Soc., 119, 4785 (1997).
11. b) T. Okuyama, Y. Ishida, and M. Ochiai, Bull. Chem. Soc. Jpn., 72, 163 (1999).
12. c) T. Okuyama, K. Sato, M. Ochiai, Chem. Lett., 1998, 1177.
13. d) T. Okuyama, H. Yamataka, and M. Ochiai, Bull. Chem. Soc. Jpn., 72, 2761 (1999).
14. e) T. Okuyama, S. Imamura, and Y. Ishida, Bull. Chem. Soc. Jpn., 74, 543 (2001).
15. T. Okuyama, T. Takino, T. Sueda, and M. Ochiai, J. Am. Chem. Soc., 117, 3360 (1995).
16. a) R. J. Hinkle and Q. A. Thomas, J. Org. Chem., 62, 7534 (1997).
17. b) R. J. HinkJe, A. J. McNeil, Q. A. Thomas, and M. N. Andrews, J. Am. Chem. Soc., 121, 7437 and 10668 (1999).
18. M. Fujita, Y. Sakanishi, and T. Okuyama, J. Am. Chem. Soc., 122, 8787 (2000).
19. +) 258.0538, found 258.0557.
20. b) W. H. Perkin and W. J. Pope, J. Chem. Soc., 99, 1510 (1911); H. Gerlach, Helv. Chim. Acta, 49, 1291 (1966); H. M. Walborsky and R. B. Banks, Bull. Soc. Chim. Belg., 89, 849 (1980).
21. b) W. H. Perkin and W. J. Pope, J. Chem. Soc., 99, 1510 (1911); H. Gerlach, Helv. Chim. Acta, 49, 1291 (1966); H. M. Walborsky and R. B. Banks, Bull. Soc. Chim. Belg., 89, 849 (1980).
22. b) W. H. Perkin and W. J. Pope, J. Chem. Soc., 99, 1510 (1911); H. Gerlach, Helv. Chim. Acta, 49, 1291 (1966); H. M. Walborsky and R. B. Banks, Bull. Soc. Chim. Belg., 89, 849 (1980).
23. c) I. Fleming and T. W. Newton, J. Chem. Soc. Perkin Trans. 1, 1984, 119.
24. d) P. J. Stang and M. Hanack, Synthesis, 1982, 85.
25. e) The ee's of the substrate and products were determined by gas chromatography using complementary three chiral columns, Chrompack-Chirasil-DEX CB, Supelco β-DEX 120, and Supelco β-DEX 325. Accuracy of the gas Chromatographic analysis was evaluated to be within ±0.5%.
26. Solvolysis was carried out in a sealed pyrex glass tube with about 2 mg of (R)-4 in 4 mL of aqueous methanol. The reaction mixture was kept at 140 °C from 4 days to a few weeks, and the products were extracted with pentane containing tetradecane as an internal standard for analysis.
27. T. Okuyama, T. Takino, K. Sato, and M. Ochiai, J. Am. Chem. Soc., 120, 2275 (1998).
28. a) M. N. Glukhovtsev, A. Pross, and L. Radom, J. Am. Chem. Soc., 116, 5961 (1994).
29. b) V. Lucchini, G. Modena, and L. Pasquato, J. Am. Chem. Soc., 117, 2297 (1995).
30. c) C. K. Kim, K. H. Hyun, C. K. Kim, and I. Lee, J. Am. Chem. Soc., 122, 2294 (2000).