octafluorobicyclo[2.2.0]hex-1(4)-ene: A greatly strained alkene with novel reactivity

Journal of the American Chemical Society

Volumn 118, Issue 39, 1996, Pages 9454-9455

  Zhang, Yin ^a   Smith, Joshua ^a   Lemal, David M ^a  

^a Dartmouth College ^*  (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE; ORGANOFLUORINE DERIVATIVE;

ARTICLE; DRUG STRUCTURE; DRUG SYNTHESIS;

EID: 0029855074     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja961656o     Document Type: Article

References (33)

1. (a) Wiberg, K. B.; Maturro, M. G.; Okarma, P. J.; Jason, M. E.; Dailey, W. P.; Burgmaier, G. J.; Bailey, W. F.; Warner, P. Tetrahedron 1986, 42, 1895.
2. (b) Wiberg, K. B.; Matturro, M. G.; Okarma, P. J.; Jason, M. E. J. Am. Chem. Soc. 1984, 106, 2194. Wiberg, K. B.; Bailey, W. F.; Jason, M. E. J. Org. Chem. 1974, 39, 3803. Casanova, J.; Rogers, H. R. J. Org. Chem. 1974, 39, 3803. Wiberg, K. B.; Burgmaier, G. J.; Warner, P. J. Am. Chem. Soc. 1971, 93, 246.
3. (b) Wiberg, K. B.; Matturro, M. G.; Okarma, P. J.; Jason, M. E. J. Am. Chem. Soc. 1984, 106, 2194. Wiberg, K. B.; Bailey, W. F.; Jason, M. E. J. Org. Chem. 1974, 39, 3803. Casanova, J.; Rogers, H. R. J. Org. Chem. 1974, 39, 3803. Wiberg, K. B.; Burgmaier, G. J.; Warner, P. J. Am. Chem. Soc. 1971, 93, 246.
4. (b) Wiberg, K. B.; Matturro, M. G.; Okarma, P. J.; Jason, M. E. J. Am. Chem. Soc. 1984, 106, 2194. Wiberg, K. B.; Bailey, W. F.; Jason, M. E. J. Org. Chem. 1974, 39, 3803. Casanova, J.; Rogers, H. R. J. Org. Chem. 1974, 39, 3803. Wiberg, K. B.; Burgmaier, G. J.; Warner, P. J. Am. Chem. Soc. 1971, 93, 246.
5. (b) Wiberg, K. B.; Matturro, M. G.; Okarma, P. J.; Jason, M. E. J. Am. Chem. Soc. 1984, 106, 2194. Wiberg, K. B.; Bailey, W. F.; Jason, M. E. J. Org. Chem. 1974, 39, 3803. Casanova, J.; Rogers, H. R. J. Org. Chem. 1974, 39, 3803. Wiberg, K. B.; Burgmaier, G. J.; Warner, P. J. Am. Chem. Soc. 1971, 93, 246.
6. Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1988, 110, 4710.
7. This paper is based principally on the Ph.D. dissertation of Y.Z., Dartmouth College, 1995.
8. Analysis of the infrared spectrum of the parent hydrocarbon 1 has shown it to be planar (ref 1a), confirming the conclusion from ab initio quantum mechanical calculations (refs 2 and 5). By demanding more p character from the central carbons, perfluoroalkyl substituents on the double bond might force pyramidalization of that bond, as is predicted for such strained alkenes as an isomer of 1, bicyclo[3.1.0]hex-1(5)-ene (refs 5 and 6). We find, however, that calculations up to the 6-31G** level predict fluorocarbon 2 to be planar like 1. These calculations were carried out with the Spartan package of programs (Hehre, W.; Wavefunction, Inc.: 18401 Von Karman, Suite 370, Irvine, CA 92717).
9. Wagner, H.-U.; Szeimes, G.; Chandrasekhar, J; Schleyer, P. v. R.; Pople, J. A.; Binkley, J. S. J. Am. Chem. Soc. 1978, 100, 1210.
10. Wiberg, K. B.; Bonneville, G.; Dempsey, R. Isr. J. Chem. 1983, 23, 85.
11. Barlow, M. G.; Haszeldine, R. N.; Morton, W. D.; Woodward, D. R. J. Chem. Soc., Perkin Trans. I 1972, 2170.
12. Camaggi, G.; Gozzo, F. J. Chem. Soc. 1969, 489.
13. Camaggi and Gozzo prepared the dichloro analog of 4 from 3 and aluminum chloride (ref 8).
14. 3): Φ -103.9 (4 exo F), -113.4 (4 endo F) (AB q, J = 219 Hz). HRMS m/e: 383.8222 (calcd 383.8219). Mp: 81.5-83 °C.
15. The reaction of 3 with aluminum iodide had been carried out earlier by Camaggi and Gozzo (ref 8), but instead of 7 they obtained its aromatic isomer.
16. 6) (AB q, J = 220.7 Hz). HRMS m/e: 429.8080 (calcd 429.8100). Mp: 79-80 °C.
17. 3): Φ -90.8 (4 exo F), -112.1 (4 endo F) (AB q, J = 216 Hz). HRMS m/e: 477.7943 (calcd 477.7962). Mp: 112.5-113.5 °C.
18. Finkelstein, H. Chem. Ber. 1910, 43, 1528.
19. HF = 7.5 Hz, 2 vinyl H), 5.35 (s, 2 bridgehead H). HRMS m/e: 292.0124 (calcd 292.0134). Mp: 124.5-126 °C.
20. 3): δ 3.95 (s, 3 H), 2.01 (s, 1 H). HRMS: 256.0132 (calcd 256.0134).
21. OH).
22. Hydration of highly fluorinated ketones is very exothermic. Guthrie, J. P. Can. J. Chem. 1975, 53, 898. Hine, J.; Flackstean, H. J. Org. Chem. 1979, 42, 177.
23. Hydration of highly fluorinated ketones is very exothermic. Guthrie, J. P. Can. J. Chem. 1975, 53, 898. Hine, J.; Flackstean, H. J. Org. Chem. 1979, 42, 177.
24. 3).
25. Eaton, P. E.; Temme, G. E., III J. Am. Chem. Soc. 1973, 95, 7508.
26. The parent [2.2.2]propellane may have been generated and trapped, although it has not been directly observed. Wiberg has shown that studies suggesting the formation of the propellane by treatment of bridgehead dihalides with reducing agents can be interpreted without intervention of the propellane (Wiberg, K. B.; Pratt, W. E.; Matturro, M. G. J. Org. Chem. 1982, 47, 2720). Generation of [2.2.2]propellane by photocyclization of 1,4-dimethylenecyclohexane has been claimed by Dannenberg et al. Dannenberg, J. J.; Prociv, T. M.; Hutt, C. J. Am. Chem. Soc. 1974, 96, 913.
27. The parent [2.2.2]propellane may have been generated and trapped, although it has not been directly observed. Wiberg has shown that studies suggesting the formation of the propellane by treatment of bridgehead dihalides with reducing agents can be interpreted without intervention of the propellane (Wiberg, K. B.; Pratt, W. E.; Matturro, M. G. J. Org. Chem. 1982, 47, 2720). Generation of [2.2.2]propellane by photocyclization of 1,4-dimethylenecyclohexane has been claimed by Dannenberg et al. Dannenberg, J. J.; Prociv, T. M.; Hutt, C. J. Am. Chem. Soc. 1974, 96, 913.
28. Parent alkene 1 dimerizes, yielding a diene which must have formed via a transient bis[2.2.2]propellane. Alkene 1 also adds to ketene to give a product which is presumably derived from an intermediate [2.2.2]propellane (ref 1).
29. +). HRMS: 296.0450 (calcd 296.0447).
30. +). HRMS: 296.0453 (calcd 296.0447).
31. For the mechanism of ring opening of [2.2.2]propellanes, see: Wiberg, K. B.; Caringi, J. J.; Matturro, M. G. J. Am. Chem. Soc. 1990, 112, 5854. Newton, M. D.; Schulman, J. M. Ibid. 1972, 94, 4391. Stohrer, W.-D.; Hoffmann, R. Ibid. 1972, 94, 779.
32. For the mechanism of ring opening of [2.2.2]propellanes, see: Wiberg, K. B.; Caringi, J. J.; Matturro, M. G. J. Am. Chem. Soc. 1990, 112, 5854. Newton, M. D.; Schulman, J. M. Ibid. 1972, 94, 4391. Stohrer, W.-D.; Hoffmann, R. Ibid. 1972, 94, 779.
33. For the mechanism of ring opening of [2.2.2]propellanes, see: Wiberg, K. B.; Caringi, J. J.; Matturro, M. G. J. Am. Chem. Soc. 1990, 112, 5854. Newton, M. D.; Schulman, J. M. Ibid. 1972, 94, 4391. Stohrer, W.-D.; Hoffmann, R. Ibid. 1972, 94, 779.