Unsaturated macrocyclic lactone synthesis via catalytic ring-closing metathesis ¹

Abstract

Ring-closing metathesis (RCM) of the terminal diene esters 2a,b with the Ru catalyst 1 results in the formation of the 20-, 21-membered macrolactones 3a,b in high yields. RCM of the diene oleate esters 4a,b with 1 gives the 19-, 20-membered macrolactones 5a,b in good yields, while an analogous reaction of the diene β,γ-unsaturated ester 6a gives the 13-membered lactone 7a in low yield.

References

1. Preliminary communication: K. E. Litinas and B. E. Salteris, presented at the 17th Hellenic Chemical Congress, Patra, 1996, Abstrs. p. 144.
2. (a) R. H. Thomson, The Chemistry of Natural Products, Blackie, Glasgow, 1986, p. 119; (b) W. B. Turner and D. C. Aldridge, Fungal Metabolites II, Academic Press, London, 1983, p. 176; (c) K. Nakanishi, T. Goto, S. Ito, S. Natori and S. Nozoe, Natural Products Chemistry, Academic Press, New York, 1974, vol. 2, p. 299.
3. (a) M. Kerschbaum, Ber. Deutsch. Chem. Ges., 1927, 60B, 902; (b) H. Brockmann and W. Henkel, Naturwissenschaften, 1950, 37, 138; (c) J. Taskinen and L. Nykanen, Acta Chem. Scand., Ser. B, 1975, 29, 757; (d) K. Hanson, J. A. O'Neill, T. J. Simpson and C. L. Willis, J. Chem. Soc., Perkin Trans. 1, 1994, 2493; (e) A. J. Carnell, G. Casy, G. Gorins, A. Kompany-Saeid, R. McCague, H. F. Olivo, S. M. Roberts and A. J. Willets, J. Chem. Soc., Perkin Trans. 1, 1994, 3431; (f) S. D. Rychnovsky and K. Hwang, J. Org. Chem., 1994, 59, 5414.
4. (a) T. Hamada, K. Daikai, R. Irie and T. Katsuki, Tetrahedron: Asymmetry, 1995, 6, 2441; (b) G. H. Vecchio and A. C. Oehlschlager, J. Org. Chem., 1994, 59, 4853; (c) C. D. J. Boden, J. Chambers and I. D. R. Stevens, Synthesis, 1993, 411; (d) E. Keinan, S. K. Sinka and S. P. Singh, Tetrahedron, 1991, 47, 4631; (e) Y. Naoshima, A. Nakamura, Y. Munakata, M. Kamezawa and H. Tachibana, Bull. Chem. Soc., Jpn., 1990, 63, 1263; (f) K. J. G. Millar, A. C. Oeschlager and J. W. Wong, J. Org. Chem., 1983, 48, 4404.
5. (a) W. Keller-Schierlein, Fortschr. Chem. Org. Naturst., 1973, 30, 313; (b) S. Masamune, G. S. Bates and J. W. Corcoran, Angew. Chem., Int. Ed. Engl., 1977, 16, 585; (c) K. C. Nicolaou, Tetrahedron, 1977, 33, 683; (d) T. G. Back, Tetrahedron, 1977, 33, 3041; (e) S. Masamune and P. A. McCarthy, in Macrolides, ed. S. Omura, Academic Press, New York, 1984, ch. 4; (f) M. M. Mansuri and I. Paterson, Tetrahedron, 1985, 41, 3569; (g) C. J. Roxburgh, Tetrahedron, 1995, 51, 9567.
6. S. Omura, Macrolide Antibiotics, Academic Press, Orlando, 1984, p. 3.
7. D. Vazquez, in Antibiotics III. Mechanism of Action of Antimicrobial and Antitumor Agents, ed. J. W. Corcoran and F. E. Hahn, Springer, New York, 1975, p. 459; M. Binder and C. Tamm, Angew. Chem., Int. Ed. Engl., 1973, 12, 370; S. B. Carter, Endeavour, 1972, 31, 77.
8. S. Abe, T. Eto and Y. Tsujito, Cosmet. Perfum., 1973, 88, 67; B. D. Mookherjee and R. A. Wilson, in Fragrance Chemistry, ed. E. T. Theimer, Academic Press, Orlando, 1982, p. 443; P. Kraft and W. Tochtermann, Liebigs Ann. Chem., 1994, 1161.
9. E. J. Corey, D. J. Brunelle and K. C. Nicolaou, J. Am. Chem. Soc., 1977, 99, 7359; L. Ruzicka and M. Stoll, Helv. Chim. Acta, 1928, 11, 1159.
10. M. Stoll and A. Rouve, Helv. Chim. Acta, 1934, 17, 1283; K. Steliou and M.-A. Poupart, J. Am. Chem. Soc., 1983, 105, 7130; E. J. Corey and K. C. Nicolaou, J. Am. Chem. Soc., 1974, 96, 5614; T. Kurihara, Y. Nakajima and O. Mitsunobu, Tetrahedron Lett., 1976, 2455; G. Voss and H. Gerlach, Helv. Chim. Acta, 1983, 66, 2994; J. Inanaga, K. Hirata, H. Saeki, T. Katsuki and M. Yamaguchi, Bull. Chem. Soc. Jpn., 1979, 52, 1989.
11. (a) B. M. Trost and T. R. Verhoeven, J. Am. Chem. Soc., 1977, 99, 3867; (b) B. M. Trost, S. Matsubara and J. J. Caringi, J. Am. Chem. Soc., 1989, 111, 8745; (c) H. J. Bestmann and R. Schobert, Angew. Chem., Int. Ed. Engl., 1983, 22, 780; (d) G. E. Keck, A. Paslani and S. F. McHardy, J. Org. Chem., 1994, 59, 3113.
12. (a) D. Villemin, Tetrahedron Lett., 1980, 21, 1715; (b) J. Tsuji and S. Hashiguchi, Tetrahedron Lett., 1980, 21, 2955; (c) J. Tsuji and S. Hashiguchi, J. Organometal. Chem., 1981, 218, 69.
13. (a) K. J. Ivin, Olefin Metathesis, Academic Press, New York, 1983; (b) R. H. Grubbs and S. H. Pine, in Comprehensive Organic Synthesis, ed. B. M. Trost, Pergamon, New York, 1991, vol. 5, ch. 9.3; (c) R. H. Grubbs, S. J. Miller and G. C. Fu, Acc. Chem. Res., 1995, 28, 446; (d) H. G. Schmalz, Angew. Chem., 1995, 107, 1981.
14. B. M. Novak and R. H. Grubbs, J. Am. Chem. Soc., 1988, 110, 960; B. M. Novak and R. H. Grubbs, J. Am. Chem. Soc., 1988, 110, 7542; R. H. Grubbs and W. Tumas, Science, 1989, 243, 907; G. C. Bazan, E. Khosravi, R. R. Schrock, W. J. Feast, V. C. Gibson, M. B. O'Regan, J. K. Thomas and W. M. Davis, J. Am. Chem. Soc., 1990, 112, 8378; G. C. Bazan, J. K. Oskam, H. C. Cho, L. Y. Park and R. R. Schrock, J. Am. Chem. Soc., 1991, 113, 6899; B. M. Novak, W. Risse and R. H. Grubbs, Adv. Polym. Sci., 1992, 102, 47; M. A. Hillmyer, C. Lepetit, D. V. McGrath, B. M. Novak and R. H. Grubbs, Macromolecules, 1992, 25, 3345; S. T. Nguyen, L. K. Johnson and R. H. Grubbs, J. Am. Chem. Soc., 1992, 114, 3974; R. R. Schrock, in Ring Opening Polymerization, ed. D. J. Brunnel, Hawer, Munich, 1993, p. 129; S. T. Nguyen and R. H. Grubbs, J. Am. Chem. Soc., 1993, 115, 9858; P. E. Schwab, M. B. France, R. H. Grubbs and J. W. Ziller, Angew. Chem., Int. Ed. Engl., 1995, 34, 2039; C. Fraser and R. H. Grubbs, Macromolecules, 1995, 28, 7248; A. W. Stumpf, E. Saive, A. Demonceau and A. F. Noels, J. Chem. Soc., Chem. Commun., 1995, 1127; M. D. Lynn, S. Kanaoka and R. H. Grubbs, J. Am. Chem. Soc., 1996, 118, 784.
15. (a) G. C. Fu and R. H. Grubbs, J. Am. Chem. Soc., 1992, 114, 5426; (b) G. C. Fu and R. H. Grubbs, J. Am. Chem. Soc., 1992, 114, 7324; (c) G. C. Fu and R. H. Grubbs, J. Am. Chem. Soc., 1993, 115, 3800; (d) G. C. Fu, S. T. Nguyen and R. H. Grubbs, J. Am. Chem. Soc., 1993, 115, 9856; (e) O. Fujimura, G. C. Fu and R. H. Grubbs, J. Org. Chem., 1994, 59, 4029; (f) S. Kim, N. Bowden and R. H. Grubbs, J. Am. Chem. Soc., 1994, 116, 1081; (g) S. J. Miller, S. Kim, Z. Chen and R. H. Grubbs, J. Am. Chem. Soc., 1995, 117, 2108; (h) S. J. Miller and R. H. Grubbs, J. Am. Chem. Soc., 1995, 117, 5855; (i) C. M. Huwe, O. C. Kiehl and S. Blechert, Synlett, 1996, 65; (j) O. Fujimura and R. H. Grubbs, J. Am. Chem. Soc., 1996, 118, 2499; (k) S. Kim, W. J. Zuercher, N. B. Bowden and R. H. Grubbs, J. Org. Chem., 1996, 61, 1073.
16. O. Fujimura, G. C. Fu, P. W. K. Rothemund and R. H. Grubbs, J. Am. Chem. Soc., 1995, 117, 2355; R. R. Schrock, J. S. Murdzek, G. C. Bazan, J. Robbins, M. DiMare and M. O'Regan, J. Am. Chem. Soc., 1990, 112, 3875; R. R. Schrock, R. T. DePue, J. Feldman, C. J. Schowerien, J. C. Dewan and A. H. Liu, J. Am. Chem. Soc., 1988, 110, 1423; A. Aguero, J. Kress and J. A. Osborn, J. Chem. Soc., Chem. Commun., 1985, 793; J. Couturier, C. Paillet, M. Leconte, J. M. Basset and K. Weiss, Angew. Chem., Int. Ed. Engl., 1992, 31, 628.
17. B. C. Borer, S. Deerenberg, H. Bierangel and U. K. Pandit, Tetrahedron Lett., 1994, 35, 3191; S. F. Martin, Y. Liao, H.-J. Chen, M. Patzel and M. N. Ramser, Tetrahedron Lett., 1994, 35, 6005; S. A. Wagman and S. F. Martin, Tetrahedron Lett., 1995, 36, 1169; A. F. Houri, Z. Xu, D. A. Cogan and A. H. Hoveyda, J. Am. Chem. Soc., 1995, 117, 2943; P. Bertinato, E. J. Sorensen, D. Meng and S. J. Danishefsky, J. Org. Chem., 1996, 61, 8000; K. C. Nicolaou, Yen He, D. Vourloumis, H. Vallberg and Z. Yang, Angew. Chem., Int. Ed. Engl., 1996, 35, 2399.
18. Preparation and characterization of catalyst 1: S. T. Nguyen, L. K. Johnson, R. H. Grubbs and J. W. Ziller, J. Am. Chem. Soc., 1992, 114, 3974; S. T. Nguyen, R. H. Grubbs and J. W. Ziller, J. Am. Chem. Soc., 1993, 115, 9858.
19. G. C. Fu, R. H. Grubbs, K. E. Litinas and S. T. Nguyen, unpublished results.
20. A. Furstner and K. Langemann, J. Org. Chem., 1996, 61, 3942.