Hydrogen shifts in cyclohexylcarbenes. Spatial dependence of activating power and of primary deuterium isotope effects

Tetrahedron

Volumn 53, Issue 44, 1997, Pages 14871-14894

  Kenar, James A ^a,b   Nickon, Alex ^a  

^a JOHNS HOPKINS UNIVERSITY   (United States)

^b NAVAL SURFACE WARFARE CENTER   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOHEXYLCARBENE DERIVATIVE; HYDRAZONE DERIVATIVE; KETONE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; ASSAY; CHEMICAL REACTION; DRUG CONFORMATION; DRUG SYNTHESIS; PHOTOLYSIS; PRIORITY JOURNAL; PROTON TRANSPORT; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030776264     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(97)10001-1     Document Type: Article

References (69)

1. (a) Kirmse, W. Carbene Chemistry, 2nd ed.; Academic: New York, 1971.
2. (b) Jones, M., Jr., Moss, R. A., Eds. Carbenes; Academic: New York, 1973; Vol. 1.
3. (c) Jones, W. M. In Rearrangements in Ground and Excited States; de Mayo, P., Ed.; Academic Press: New York, 1980; Vol. 2, pp 95-160.
4. Nickon, A. Acc. Chem. Res. 1993, 26, 84-89.
5. Kenar, J. A.; Nickon, A. Tetrahedron Lett. 1994, 35, 9657-9660.
6. (a) Stern, A. G.; Ilao, M. C.; Nickon, A. Tetrahedron, 1993, 49, 8107-8118.
7. (b) Nickon, A.; Stern, A. G.; Ilao, M. C. Tetrahedron Lett. 1993, 34, 1391-1394.
8. (c) Stern, A. G. Ph.D. Thesis, The Johns Hopkins University, 1986.
9. Kyba, E. P. J. Am. Chem. Soc. 1977, 99, 8330-8332.
10. (a) Evanseck, J. D.; Houk, K. N. J. Am. Chem. Soc. 1990, 112, 9148-9156.
11. (b) For recent calculations involving rearrangements of dialkylcarbenes, including ethylmethylcarbene, see Sulzbach, H. M.; Platz, M. S.; Schaefer, H. F.; Hadad, C. M. J. Am. Chem. Soc. 1997, 119, 5682-5689.
12. Press, L. S.; Shechter, H. J. Am. Chem. Soc. 1979, 101, 509-510.
13. Segher, L.; Shechter, H. Tetrahedron Lett. 1976, 1943-1946.
14. For full details and calculations see Kenar, J. A. Ph. D. Thesis, Johns Hopkins University, 1994.
15. Beckwith, A.L.J.; Easton, C.J. Chem. Soc. Perkin Trans. 2 1983, 5, 661-668.
16. Corey, E. J.; Enders, D. Chem. Ber. 1978, 111, 1337-1361.
17. Fang, J. M.; Sund, S. F.; Rei, M. H. J. Chem. Soc. Perkin Trans 2 1989, 7, 747-750.
18. For a discussion of 1,3-allylic strain interactions see: (a) Hoffmann, R. W. Chem. Rev. 1989, 89, 1841-1860.
19. (b) Fraser, R. R.; Banville, J.; Dhwawan, K. L. J. Am. Chem. Soc. 1978, 100, 7999-8001.
20. (c) Broeker, J. L.; Hoffmann, R. W.; Houk, K. N. J. Am. Chem. Soc. 1991, 113, 5006-5017.
21. Enders, D.; Plant, A. Synlett 1990, 12, 725-726.
22. For examples of dimethylhydrazone isomerizations see Davenport, K. G.; Eichenauer, H.; Enders, D.; Newcomb, M.; Bergbreiter, D. E. J. Am. Chem. Soc. 1979, 101, 5654-5659.
23. Bertz, S. H.; Dabbagh, G. J. Org. Chem. 1983, 48, 116-119.
24. (a) Garner, C. M.; Mossman, B. C.; Prince, M. E. Tetrahedron Lett. 1993, 34, 4273-4276.
25. (b) Mullica, D. F.; Garner, C. M.; Prince, M. E.; Mossman, B. C.; Sappenfield, E. L. J. Cryst. Spectro. Res. 1992, 22, 515-522.
26. Paquette, L. A.; Barth, W. J. Org. Chem. 1985, 50, 2438-2443.
27. 4 separated the chemical shifts and sharpened the signals for the ax and eq Me groups of the tosylhydrazones.
28. Freeman, P. K.; Balyeat, J. R. J. Org. Chem. 1977, 19, 3205-3206.
29. For example, menthone tosylhydrazone α-epimerizes 150 times faster than does the parent menthone (ref. 17). For other cases of epimerization in tosylhydrazones see: (a) References 18.
30. (b) Casanova, J.; Zahra, J. P. Tetrahedron Lett. 1977, 21, 1773-1776.
31. (c) Hutchins, R. O.; Milewski, C A.; Maryanoff, B. E. J. Am. Chem. Soc. 1973, 95, 3662-3668.
32. (d) Paquette, L. A.; Ross, R. J.; Shi, Y-J. J. Org. Chem. 1990, 55, 1589-1598.
33. (e) Nakai, T.; Mimura, T. Tetrahedron Lett. 1979, 6, 531-534.
34. (f) Satyanarayana, N.; Nayak, U. R. Indian J. Chem, Sect. B 1986, 25B, 28-31.
35. (g) Tavernier, D.; Hosten, N.; Anteunis, M. Synthesis 1979, 8, 613-614.
36. (h) Caporusso, A. M.; Giacomelli, G.; Lardicci, L. J. Chem. Soc. Perkin Trans 1 1979, 12, 3139-3145.
37. Fuchs, P. L.; Bunnell, C. A. J. Org. Chem. 1977, 42, 2614-2617.
38. (a) Johnson, F.; Duquette, L. G.; Whitehead, A.; Dorman, L. C. Tetrahedron 1974, 50, 3241-3251.
39. (b) Pasto, D. J.; Johnson, C. R. "Organic Structure Determination," Prentice-Hall, New Jersey, 1969, 174-175.
40. Schwab, F. C.; Brandolini, A. J. Macromolecules 1989, 22, 2538-2540.
41. Bamford, W. R.; Stevens, T. S. J. Chem. Soc. C 1952, 4735-4740.
42. For reviews of the Bamford-Stevens reaction see: (a) References 1a and 1b.
43. (b) Regitz, M.; Maas, G. Diazo Compounds, Academic: New York, 1986, pp 257-295.
44. For the Shapiro reaction see Chamberlin, R. A.; Bloom, S. H. Org. Reactions 1990, 39, 1-83 and references cited there.
45. (a) Nickon, A.; Huang, F.-C.; Weglein, R.; Matsuo, K.; Yagi, J. J. Am. Chem. Soc. 1974, 96, 5264-5265.
46. (b) Nickon, A.; Zurer, P. St. J. J. Org. Chem. 1981, 46, 4685-4694.
47. (c) For bystander effects on the rates of H shifts in laser flash photolyses of halodiazirines see Liu, M. T. H.; Bonneau, R. J. Am. Chem. Soc. 1996, 118, 8098-8101, and references cited there.
48. Kyba, E. P.; John. A. M. J. Am. Chem. Soc. 1977, 99, 8329-8330.
49. For other examples in carbene chemistry see: (a) Ref. 27.
50. (b) Kyba, E. P.; Hudson, C. W. J. Org. Chem. 1977, 42, 1935-1939.
51. (c) Freeman, P. K.; Hardy, T. A.; Balyeat, J. R.; Westcott, L. D. Jr. J. Org. Chem. 1977, 42, 3356-3359. For examples in other reactions see:
52. (d) Agosta, W. C.; Wolff, S. J. Am. Chem. Soc. 1976, 98, 4316-4317.
53. (e) Nickon, A.; Werstiuk, N. H. J. Am. Chem. Soc. 1967, 89, 3917-3918.
54. (f) Nickon, A.; Werstiuk, N. H. J. Am. Chem. Soc. 1972, 94, 7081-7086.
55. (g) Corey, E. J.; Sneen, R. A. J. Am. Chem. Soc. 1956, 78, 6269-6278.
56. 3-type throughout the rearrangement.
57. That 3° and 2° H's do not differ markedly in their isotopic behavior is suggested by the recent finding of Moss et al. that the primary kinetic isotope effect for shift of the 3° H(D) in cyclobutylfluorocarbene generated by thermolysis of the corresponding diazirine at 138° C is ca. 2.50 [Moss, R. A.; Xue, S.; Ma, W. Tetrahedron Lett. 1996, 37, 1929-1932]. Their value is in the range of those found for 2° H(D)'s (Table 3).
58. eq migration ratios for thermal cases become increased by a factor of 1.24. Thus, the migration ratio of 1.73 obtained from studies on the homobrexyl system (last compound in Table 3) now becomes 2.15. (The adjustment factor for photolytic B.S. cases would be the square root of 1.44 , namely 1.20). To avoid confusion as to the sources of all numerical data we have not rounded off any of the original numbers or the adjusted ones. However, in view of the experimental errors involved, readers should regard the data as less quantitative than indicated.
59. ax to adopt a more equatorial-like geometry.
60. Fraser, R. R.; Champagne, P. J. Can. J. Chem. 1980, 58, 72-78.
61. For commentary and references to isotope effects in carbene rearrangements see ref. 31 and reviews by: (a) Platz, M. S.; Modarelli, D. A.; Morgan, S.; White, W. R.;Mullins, M.; Celebi, S.; Toscano, J. P. Prog. Reac. Kin. 1994, 19, 93-137.
62. (b) Liu, M. T. H. Acc. Chem. Res. 1994, 27, 287-294.
63. (c) Jackson, J. E.; Platz, M. S. in Advances in Carbene Chemistry, Brinker, U. H., Ed.; JAI Press, Greenwich, CT, Vol 1, 1994, pp 89-160.
64. ax (by a factor of 4.4). Nickon, A.; Ilao, M. C.; Stern, A. G.; Summers, M. F. J. Am. Chem. Soc. 1992, 114, 9230-9232.
65. (a) Modarelli, D. A.; Morgan, S.; Platz, M.S. J. Am. Chem. Soc. 1992, 114, 7034-7041 and references cited there.
66. (b) Seburg, R. A.; McMahon, R. J. J. Am. Chem. Soc. 1992, 114, 7183-7189.
67. (c) Fox, J. M.; Scacheri, J. E. G.; Jones, K. G. L.; Jones, M. Jr. Tetrahedron Lett. 1992, 33, 5021-5024.
68. Robson, J. H.; Shechter, H. J. Am. Chem. Soc. 1967, 89, 7112-7114.
69. 1H NMR assignments for 1c and 1d see reference 12 and House, H. O.; Tefertiller, B. A.; Olmstead, H. D. J. Org. Chem. 1968, 33, 935-942.