Kinetics and mechanism of cyclopropanation of cyclooctene by [Fe(η5-C5H5)(CO)2CH 2SPh2]BF4

Organometallics

Volumn 17, Issue 21, 1998, Pages 4645-4648

  McCarten, Paul ^a   Barefield, E Kent ^a  

^a GEORGIA INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001068042     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om980472a     Document Type: Article

References (32)

1. An exhaustive review of Helquist's work on these reagents and of other methods of cyclopropanation of alkenes up to 1987 is given in: O'Connor, E. J.; Brandt, S.; Helquist, P. J. Am. Chem. Soc. 1987, 109, 3739.
2. This compound is currently available from Aldrich Chemical Co., and its preparation and procedures for cyclopropanation have appeared in: Organic Syntheses; Mattson, M. N.; O'Connor, E. J.; Helquist, P. Org. Synth. 1992, 70, 177.
3. This compound is currently available from Aldrich Chemical Co., and its preparation and procedures for cyclopropanation have appeared in: Organic Syntheses; Mattson, M. N.; O'Connor, E. J.; Helquist, P. Org. Synth. 1992, 70, 177.
4. 3Si, (f) R. M.; Theys, R. D.; Hossain, M. M. J. Am. Chem. Soc. 1992, 114, 777.
5. 3Si, (f) R. M.; Theys, R. D.; Hossain, M. M. J. Am. Chem. Soc. 1992, 114, 777.
6. 3Si, (f) R. M.; Theys, R. D.; Hossain, M. M. J. Am. Chem. Soc. 1992, 114, 777.
7. 3Si, (f) R. M.; Theys, R. D.; Hossain, M. M. J. Am. Chem. Soc. 1992, 114, 777.
8. 3Si, (f) R. M.; Theys, R. D.; Hossain, M. M. J. Am. Chem. Soc. 1992, 114, 777.
9. 3Si, (f) R. M.; Theys, R. D.; Hossain, M. M. J. Am. Chem. Soc. 1992, 114, 777.
10. (a) Casey, C. P.; Miles, W. H.; Tuikada, H.; O'Connor, J. M. J. Am. Chem. Soc. 1982, 104, 3761.
11. (b) Kremer, K. A. M.; Kuo, G. H.; O'Connor, E. J.; Helquist, P.; Kerber, R. C. J. Am. Chem. Soc. 1982, 104, 9.
12. (c) Kuo, G. H.; Helquist, P.; Kerber, R. C. Organometallics 1984, 3, 806.
13. (d) Casey, C. P.; Miles, W. H.; Tukada, H. J. Am. Chem. Soc. 1985, 107, 2924.
14. +" (ref 3b and references cited).
15. +" (ref 3b and references cited).
16. + (Kremer, K. A. M.; Helquist, P. J. Organomet. Chem. 1985, 285, 231), but see ref 1 for alternative mechanistic considerations.
17. The efficiency of such a process would likely be limited, although the extent of bond breaking in the transition state would be very important. It would also be inefficient in that the chiral center would be lost upon displacement of the sulfide.
18. + are cited.
19. Barefield, E. K.; McCarten, P.; Hillhouse, M. C. Organometallics 1985, 4, 1682.
20. Perrin, D. D.; Armarego, W. L. F.; Perrin, D. R. Purification of Laboratory Chemicals; Pergamon Press Ltd: Oxford, 1966.
21. 1H NMR spectra with those of authentic materials. Bicyclo[6.1.0]nonane, prepared according to the procedure given by Simmons, H. E.; Cairns, T. L.; Vladuchick, S. A.; Hoiness, C. M. Org. React. 1973, 20, 1, was provided by James G. Davidson. 1-Methylcyclooctene was obtained from Aldrich Chemical Co.
22. Brookhart, M.; Tucker, J. R.; Husk, G. R. J. Am. Chem. Soc. 1983, 105, 258.
23. The actual concentrations of diphenylsulfide are less than the number of equivalents indicated by a factor of 0.424/0.434. The correct molar concentrations were used in all calculations of rate constants.
24. 4) used in constructing Figures 1 and 2 are 0.89 ± 0.09, 1.21 ± 0.09, 1.25 ± 0.07, 1.58 ± 0.02, 1.66 ± 0.04, 2.03 ± 0.12, 2.50 ± 0.01, 2.93 ± 0.17, and 3.35 ± 0.09.
25. Cutler, A.; Ehntholt, D.; Giering, W. P.; Lennon, P.; Raghu, S.; Rosan, A.; Rosenblum, M.; Tancrede, J.; Wells, D. J. Am. Chem. Soc. 1976, 98, 3495.
26. 2 is dimensionless, as it is the ratio of second-order rate constants.
27. +; see reference 1.
28. Adams, W.; Birke, A.; Cadiz, C.; Diaz, S.; Rodriquez, A. J. Org. Chem. 1978, 43, 1154.
29. Casey, C. P.; Polichnowski, S. W.; Schusterman, A. J.; Jones, C. R. J. Am. Chem. Soc. 1979, 101, 7282.
30. Friedrich, E. C.; Domek, J. M.; Pong, R. Y. J. Org. Chem. 1985, 50, 4640.
31. 4 appears to be nitromethane; see ref 1 and also Bäckvall, J.-E.; Löfström, C.; Juntunen, S. K.; Mattson, M. Tetrahedron Lett. 1993, 34, 2007.
32. + is second order: Merrifield, J. H.; Lin, G.-Y.; Kiel, W. A.; Gladysz, J. A. J. Am. Chem. Soc. 1983, 105, 5811.