Catalytic ring closing metathesis of dienynes: Construction of fused bicyclic [n.m.0] rings

Journal of Organic Chemistry

Volumn 61, Issue 3, 1996, Pages 1073-1081

  Kim, Soong Hoon ^a   Zuercher, William J ^a   Bowden, Ned B ^a   Grubbs, Robert H ^a  

^a California Institute of Technology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001354464     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo951648a     Document Type: Article

References (41)

1. See, for instance: Natural Products Chemistry; Nakanishi, K., Ed.; Academic Press: New York. 1974; Vols. 1-3.
2. Preliminary work was reported in a communication. Kim, S. H.; Bowden, N.; Grubbs, R. H. J. Am. Chem. Soc. 1994, 116, 10801.
3. For the preparation and characterization of catalyst 1: (a) Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1992, 114, 3974.
4. (b) Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1993, 115, 9858.
5. Previous reports on RCM from this laboratory: (a) Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 5426. (b) Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 7324.
6. Previous reports on RCM from this laboratory: (a) Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 5426. (b) Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 7324.
7. (c) Fu, G. C.; Grubbs, R. H. J Am. Chem. Soc. 1993, 115, 3800.
8. (d) Fu, G. C.; Nguyen, S. T.; Grubbs, R. H J. Am. Chem. Soc. 1993, 115, 9856.
9. (e) Fujimura, O.; Fu, G. C.; Grubbs, R. H. J. Org. Chem. 1994, 59, 4029.
10. (f) Miller, S. J.; Kim, S. H.; Chen, Z.; Grubbs, R. H. J. Am. Chem. Soc. 1995, 117, 2108.
11. (g) Miller, S. J.; Grubbs, R. H. J. Am. Chem. Soc. 1995, 117, 5855-5856.
12. (h) Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-452. For recent applications of RCM to natural product synthesis
13. (i) Martin, S. F.; Liao, Y.; Rein, T. Tetrahedron Lett 1994, 35, 691.
14. (j) Borer, B. C.; Deerenberg, S.; Bieraugel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191.
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16. (l) Houri, A. F.; Xu, Z.; Logan, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 2943. For a review on applications of olefin metathesis in organic synthesis:
17. Grubbs, R. H.; Pine, S. H. In Comprehensive Organic Synthesis, Trost, B. M., Ed.; Pergamon: New York, 1991; Vol. 5, Chapter 9.3.
18. Katz, T. J.; Sivavec, T M. J. Am. Chem. Soc. 1985, 107, 737.
19. (a) Korkowski, P. F.; Hoye, T. R.; Rydberg, D. B. J. Am. Chem. Soc. 1988, 110, 2676.
20. (b) Harvey, D. F.; Brown, M. F. J. Org. Chem. 1992, 57, 5059. For a review on the chemistry of Fischer carbenes with ene-yne substrates see: Wulff, W. D. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon: New York, 1991; Vol. 5, Chapter 9.2.
21. (b) Harvey, D. F.; Brown, M. F. J. Org. Chem. 1992, 57, 5059. For a review on the chemistry of Fischer carbenes with ene-yne substrates see: Wulff, W. D. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon: New York, 1991; Vol. 5, Chapter 9.2.
22. Hoye, T. R.; Dinsmore, C. J. J. Am. Chem. Soc. 1991, 113, 4343.
23. Some substrates possess specific structural requirements such as pre-formed carbenes and specific α-diazocarbonyl compounds.
24. For instance, the rhodium-catalyzed reaction showed a complex product distribution arising from several competing processes (ref 7).
25. The dienyne cyclization shown in Scheme 2 required a stoichiometric amount of pre-formed Fischer carbene (ref 6a).
26. 2Br, DMF
27. The possibility that the first step involves an alkyne metathesis followed by two diene RCM steps cannot be ruled out. However, later experiments favor the proposed mechanism (see text).
28. Dienyne RCM proceeds at a somewhat slower rate with the free alcohols.
29. NMR reactions were conducted in 0.2-0.3 mmol scale at 0.01-0.07 M substrate concentration.
30. 3) (34): (a) Schrock, R. R.; DePue, R. T.; Feldman, J.; Schaverien, C. J.; Dewan, J. C.; Liu, A. H. J. Am. Chem. Soc. 1988, 110, 1423.
31. (b) Schrock, R. R.; DePue, R. T.; Feldman, J.; Yap, K. B.; Yang, D. C.; Davis, W. M.; Park, L.; DiMare, M.; Schofield, M.; Anhaus, J.; Walborsky, E.; Evitt, E.; Kruger, C.; Betz, P. Organometallics 1990, 9, 2262.
32. 3) (35): Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. J. Am. Chem. Soc. 1990, 112, 3875.
33. (d) Bazan, G. C.; Oskam, J. H.; Cho, H.-N.; Park, L. Y.; Schrock, R. R. J. Am. Chem. Soc. 1991, 113, 6899. Both the tungsten 34 and molybdenum 35 alkylidenes have been successfully employed for diene RCM (ref 4 and Grubbs, R. H., unpublished results).
34. Hofmeister, H.; Annen, K.; Laurent, H.; Wiechert, R. Angew. Chem., Int. Ed. Engl. 1984, 23, 727-729.
35. 6 with 3-5 mol % catalyst.
36. Catalyst 1 fails to metathesize vinyl halide species as well. Kim, S.-H.; Grubbs, R. H. Unpublished results.
37. Dias, E. L.; Grubbs, R. H. Unpublished results.
38. 16b only unreacted starting material was recovered. (a) Couturier, J.-M.; Pailet, C.; Leconte, M.; Basset, J.-M.; Weiss, K. Angew. Chem., Int. Ed. Engl. 1992, 31, 628.
39. (b) Tebbe, F. N.; Parshall, G. W.; Overall, D. W. J. Am. Chem. Soc. 1979, 101, 5074.
40. Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43, 2923.
41. Nahm, S.; Weinreb, S. M. Tetrahedron Lett. 1981, 22, 3815-3818.