Rearrangements of substituted 3-aza-1,2,5-hexatrienes. 3. The scope and versatility of an extremely mild 3-aza-Cope reaction

Journal of Organic Chemistry

Volumn 61, Issue 1, 1996, Pages 55-62

  Walters, Michael A ^a   Hoem, Andrew B ^a   McDonough, Colleen S ^a  

^a Dartmouth College   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0002438496     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo951587g     Document Type: Article

References (54)

1. For reviews concerned with these and related [3,3]-sigmatropic rearrangements, see the following: (a) Ziegler, F. E. Chem. Rev. 1988, 88, 1423. (b) Blechert, S. Synthesis 1989, 89, 71. (c) Lutz, R. P. Chem. Rev. 1984, 84, 205. The ester enolate Claisen and the oxy-Cope reactions are perhaps the best examples of research directed along these lines. For general discussions of these processes, see: (d) Wipf, P. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Elmsford, NY, 1991; Vol. 5, pp 827-873, and (e) Bronson, J. J.; Danheiser, R. L. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Elmsford, NY, 1991; Vol. 5, pp 999-1035.
2. For reviews concerned with these and related [3,3]-sigmatropic rearrangements, see the following: (a) Ziegler, F. E. Chem. Rev. 1988, 88, 1423. (b) Blechert, S. Synthesis 1989, 89, 71. (c) Lutz, R. P. Chem. Rev. 1984, 84, 205. The ester enolate Claisen and the oxy-Cope reactions are perhaps the best examples of research directed along these lines. For general discussions of these processes, see: (d) Wipf, P. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Elmsford, NY, 1991; Vol. 5, pp 827-873, and (e) Bronson, J. J.; Danheiser, R. L. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Elmsford, NY, 1991; Vol. 5, pp 999-1035.
3. For reviews concerned with these and related [3,3]-sigmatropic rearrangements, see the following: (a) Ziegler, F. E. Chem. Rev. 1988, 88, 1423. (b) Blechert, S. Synthesis 1989, 89, 71. (c) Lutz, R. P. Chem. Rev. 1984, 84, 205. The ester enolate Claisen and the oxy-Cope reactions are perhaps the best examples of research directed along these lines. For general discussions of these processes, see: (d) Wipf, P. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Elmsford, NY, 1991; Vol. 5, pp 827-873, and (e) Bronson, J. J.; Danheiser, R. L. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Elmsford, NY, 1991; Vol. 5, pp 999-1035.
4. For reviews concerned with these and related [3,3]-sigmatropic rearrangements, see the following: (a) Ziegler, F. E. Chem. Rev. 1988, 88, 1423. (b) Blechert, S. Synthesis 1989, 89, 71. (c) Lutz, R. P. Chem. Rev. 1984, 84, 205. The ester enolate Claisen and the oxy-Cope reactions are perhaps the best examples of research directed along these lines. For general discussions of these processes, see: (d) Wipf, P. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Elmsford, NY, 1991; Vol. 5, pp 827-873, and (e) Bronson, J. J.; Danheiser, R. L. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Elmsford, NY, 1991; Vol. 5, pp 999-1035.
5. For reviews concerned with these and related [3,3]-sigmatropic rearrangements, see the following: (a) Ziegler, F. E. Chem. Rev. 1988, 88, 1423. (b) Blechert, S. Synthesis 1989, 89, 71. (c) Lutz, R. P. Chem. Rev. 1984, 84, 205. The ester enolate Claisen and the oxy-Cope reactions are perhaps the best examples of research directed along these lines. For general discussions of these processes, see: (d) Wipf, P. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Elmsford, NY, 1991; Vol. 5, pp 827-873, and (e) Bronson, J. J.; Danheiser, R. L. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon Press: Elmsford, NY, 1991; Vol. 5, pp 999-1035.
6. (a) Kurth, M. J.; Brown, E. G. Synthesis 1988, 362.
7. (b) Kurth, M. J.; Decker, O. H. W.; Hope, H.; Yanuck, M. D. J. Am. Chem. Soc. 1985, 107, 443.
8. (c) Kurth, M. J.; Decker, O. H. W. J. Org. Chem. 1985, 50, 5769.
9. (d) Kurth, M. J.; Decker, O. H. W. Tetrahedron Lett. 1983, 24, 4535.
10. (e) Ireland, R. E.; Willard, A. K. J. Org. Chem. 1974, 39, 421.
11. (f) Hill, R. K.; Gilman, N. W. Tetrahedron Lett. 1967, 1421.
12. (g) Hill, R. K.; Newkome, G. R. Tetrahedron Lett. 1968, 5059.
13. (h) Tsunoda, T.; Tatsuki, S.; Akasaka, M.; Itô, S. Tetrahedron Lett. 1993, 3297.
14. (i) Tsunoda, T.; Sakai, M.; Sasaki, O.; Sako, Y.; Hondo, Y.; Itô, S. Tetrahedron Lett. 1992, 33, 1651.
15. (j) Tsunoda, T.; Sasaki, O.; Itô, S. Tetrahedron Lett. 1990, 31, 727.
16. (a) Gilbert, J. C.; Senaratne, K. P. A. Tetrahedron Lett. 1984, 25, 2303.
17. (b) Brannock, K. C.; Burpitt, R. D. J. Org. Chem. 1961, 20, 3576.
18. (c) Corbier, J.; Cresson, P. C. R. Seances Acad. Sci., Ser. C 1970, 270, 2077.
19. (d) Barta, N. S.; Cook, G. R.; Landis, M. S.; Stille, J. R. J. Org. Chem. 1992, 57, 7188.
20. (e) Danishefsky, S. J.; Phillips, G. B. Tetrahedron Lett. 1984, 25, 3159.
21. (f) Hill, R. K. Tetrahedron. Lett. 1978, 4337.
22. (g) Bailey, P. D.; Harrison, M. J. Tetrahedron Lett. 1989, 30, 5341.
23. (h) Cook, G. R.; Barta, N. S.; Stille, J. R. J. Org. Chem. 1992, 57, 461.
24. (i) Beholz, L. G.; Stille, J. R. J. Org. Chem. 1993, 58, 5095. The use of a Pd(0) catalyst to effect this transformation has also been reported.
25. (j) Murahashi, S. I.; Makabe, Y. Tetrahedron Lett. 1985, 26, 5563.
26. (k) Murahashi, S. I.; Makabe, Y.; Kunita, K. J. Org. Chem. 1988, 53, 4489.
27. Exceptions to this temperature range have been observed. (a) Welch, J T.; De Corte, B.; De Kimpe, N. J. Org. Chem. 1990, 55, 4981. Zwitterionic 3-aza-Cope examples have also been reported to occur at lower temperatures: (b) Vedejs, E.; Gingras, M. J. Am. Chem. Soc. 1994, 116, 579. (c) Nubbemeyer, U. J. Org. Chem. 1995, 60, 3773.
28. Exceptions to this temperature range have been observed. (a) Welch, J T.; De Corte, B.; De Kimpe, N. J. Org. Chem. 1990, 55, 4981. Zwitterionic 3-aza-Cope examples have also been reported to occur at lower temperatures: (b) Vedejs, E.; Gingras, M. J. Am. Chem. Soc. 1994, 116, 579. (c) Nubbemeyer, U. J. Org. Chem. 1995, 60, 3773.
29. Exceptions to this temperature range have been observed. (a) Welch, J T.; De Corte, B.; De Kimpe, N. J. Org. Chem. 1990, 55, 4981. Zwitterionic 3-aza-Cope examples have also been reported to occur at lower temperatures: (b) Vedejs, E.; Gingras, M. J. Am. Chem. Soc. 1994, 116, 579. (c) Nubbemeyer, U. J. Org. Chem. 1995, 60, 3773.
30. Brannock, K. C.; Burpitt, R. D. J. Org. Chem. 1965, 30, 2564.
31. Ab initio calculations confirm this as a reasonable hypothesis. See: Walters, M. A. J. Am. Chem. Soc. 1994, 116, 11618-11619.
32. (a) Walters, M. A.; McDonough, C. S.; Brown, P. S., Jr ; Hoem, A B. Tetrahedron Lett. 1991, 32, 179.
33. (b) Walters, M. A.; Hoem, A. B.; Arcand, H R.; Hegman, A. D.; McDonough, C. S. Tetrahedron Lett. 1993, 34, 1453
34. (c) Walters, M. A.; Hoem, A. B. J. Org. Chem. 1994, 59, 2645.
35. (a) Molina, P.; Alajarin, M.; Lopez-Leonardo, C.; Alcantara, J. Tetrahedron 1993, 5153.
36. (b) Molina, P.; Alajarin, M.; Lopez-Leonardo, C. Tetrahedron Lett. 1991, 32, 4041.
37. Nubbemeyer, U. Synthesis 1993, 1120.
38. Bruckner, R.; Huisgen, R. Tetrahedron Lett. 1994, 35, 3281.
39. (a) Appel, R.; Warning, K.; Ziehn, K.-D. Chem. Ber. 1973, 106, 3450.
40. (b) Yamato, E.; Sugasawa, S. Tetrahedron Lett. 1970, 4383.
41. For a review of the synthesis of ketenimines, see: Krow, G. R. Angew. Chem., Int. Ed. Engl. 1971, 10, 435.
42. Eckert, H.; Forster, B. Angew. Chem., Int. Ed. Engl. 1987, 26, 894-895.
43. Saraie, T.; Ishiguro, T.; Kawashima, K.; Morita, K. Tetrahedron Lett. 1973, 2121.
44. For a review of the Mitsunobu reaction, see: Mitsunobu, O. Synthesis 1981, 1.
45. Bestmann, H. J.; Lienert, J.; Mott, L. Liebigs Ann. Chem. 1968, 718, 24-32.
46. The mixture of nitrile isomers 13 was converted to one isomer by treatment with mild acid or silica gel.
47. House, H. O.; Lubinkowski, J.; Good, J. J. J. Org. Chem. 1975, 40, 862.
48. [2,3]-Sigmatropic rearrangements evince a similar preference for bond formation on the equatorial face of the cyclohexane system. (a) Evans, D. A.; Sims, C. L.; Andrews, G. C. J. Am. Chem. Soc. 1977, 99, 5453. (b) Mander, L. N.; V., T. J. Aust. J. Chem. 1980, 33, 1559-1568.
49. [2,3]-Sigmatropic rearrangements evince a similar preference for bond formation on the equatorial face of the cyclohexane system. (a) Evans, D. A.; Sims, C. L.; Andrews, G. C. J. Am. Chem. Soc. 1977, 99, 5453. (b) Mander, L. N.; V., T. J. Aust. J. Chem. 1980, 33, 1559-1568.
50. Clarke, L. F.; Hegarty, A. F. J. Org. Chem. 1992, 57, 1940 and references cited therein.
51. This concept has been employed to explain the effect of substituent conformation on a closely analogous reaction, that of the formation of exocyclic alkenes by elimination of HBr. For example, cis-4-tert-butylcyclohexanemethyl bromide (axial) undergoes elimination to 1-tert-butyl-4-methylenecyclohexane at a rate nine times faster than does the corresponding trans (equatorial) epimer. King, J. F.; Coppen, M. J. Can. J. Chem. 1971, 49, 3714-3723. We thank a referee for bringing this concept to our attention.
52. 1H) consistent with the presence of an aldehyde which we presumed to be 29. Attempts to isolate this compound from the crude mixture were unsuccessful.
53. Cross, B.; Whitham, G. H. J. Chem. Soc. 1960, 3895.
54. This proposed mechanism is reminiscent of a published synthetic process in which the allylic deprotonation of nonenolizable N-allyl imidoyl chlorides is found to lead to good yields of substituted pyrroles. Engel, N.; Steglich, W. Angew. Chem., Int. Ed. Engl. 1978, 17, 676.