Palladium(II)-Catalyzed Dehydrative Cyclization of cis-4-Alkylcycloalken-2-ols. Synthesis of Tricyclic Spiroketals in a One-Pot Sequence

Synlett

Volumn 1996, Issue 6, 1996, Pages 576-578

  Tenaglia, Alphonse ^a   Kammerer, Françoise ^a  

^a AIX MARSEILLE UNIVERSITY   (France)

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Indexed keywords

EID: 0008528765     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1996-5481     Document Type: Article

References (20)

1. Tenaglia, A.; Le Brazidec, J.-Y.; Souchon, F. Tetrahedron Lett. 1995, 36, 4241-4244.
2. The requisite 1,4-cis-disubstituted cycloalk-2-enes were obtained via Pd-catalyzed regio- and stereoselective alkylation of cycloalkadiene monoepoxides. Cf a) Trost, B. M.; Molander, G. A. J. Am. Chem. Soc. 1981, 103, 5969. b) Tsuji, J.; Kataoka, H.; Kobayashi, Y. Tetrahedron Lett. 1981, 22, 2575.
3. The requisite 1,4-cis-disubstituted cycloalk-2-enes were obtained via Pd-catalyzed regio- and stereoselective alkylation of cycloalkadiene monoepoxides. Cf a) Trost, B. M.; Molander, G. A. J. Am. Chem. Soc. 1981, 103, 5969. b) Tsuji, J.; Kataoka, H.; Kobayashi, Y. Tetrahedron Lett. 1981, 22, 2575.
4. 2 were reported for the cleavage of cyclic acetals by transketalization. Cf Lipschutz, B. H.; Pollart, D.; Monforte, J.; Kotsuki, H. Tetrahedron Lett. 1985, 26, 705.
5. Palladium(II) salts associated (or not) to reoxidizing agents are known to catalyze heterocyclic syntheses via intramolecular addition of heteronucleophiles to double bonds. Cf, for instance: a) Hosokawa, T.; Murahashi, S.-I. Heterocycles 1992, 33, 1079. b) Tamaru, Y.; Yoshida, Z.-i. J. Organometal. Chem. 1987, 334, 213. c) Masanari, K.; Harayama, H.; Tanaka, S.; Tamaru, Y. J. Chem. Soc., Chem. Commun. 1994, 2531. d) Compain, P.; Vatèle, J.-M.; Goré, J. Synlett 1994, 943.
6. Palladium(II) salts associated (or not) to reoxidizing agents are known to catalyze heterocyclic syntheses via intramolecular addition of heteronucleophiles to double bonds. Cf, for instance: a) Hosokawa, T.; Murahashi, S.-I. Heterocycles 1992, 33, 1079. b) Tamaru, Y.; Yoshida, Z.-i. J. Organometal. Chem. 1987, 334, 213. c) Masanari, K.; Harayama, H.; Tanaka, S.; Tamaru, Y. J. Chem. Soc., Chem. Commun. 1994, 2531. d) Compain, P.; Vatèle, J.-M.; Goré, J. Synlett 1994, 943.
7. Palladium(II) salts associated (or not) to reoxidizing agents are known to catalyze heterocyclic syntheses via intramolecular addition of heteronucleophiles to double bonds. Cf, for instance: a) Hosokawa, T.; Murahashi, S.-I. Heterocycles 1992, 33, 1079. b) Tamaru, Y.; Yoshida, Z.-i. J. Organometal. Chem. 1987, 334, 213. c) Masanari, K.; Harayama, H.; Tanaka, S.; Tamaru, Y. J. Chem. Soc., Chem. Commun. 1994, 2531. d) Compain, P.; Vatèle, J.-M.; Goré, J. Synlett 1994, 943.
8. Palladium(II) salts associated (or not) to reoxidizing agents are known to catalyze heterocyclic syntheses via intramolecular addition of heteronucleophiles to double bonds. Cf, for instance: a) Hosokawa, T.; Murahashi, S.-I. Heterocycles 1992, 33, 1079. b) Tamaru, Y.; Yoshida, Z.-i. J. Organometal. Chem. 1987, 334, 213. c) Masanari, K.; Harayama, H.; Tanaka, S.; Tamaru, Y. J. Chem. Soc., Chem. Commun. 1994, 2531. d) Compain, P.; Vatèle, J.-M.; Goré, J. Synlett 1994, 943.
9. Baldwin, J. E.; Lusch, M. J. Tetrahedron 1982, 38, 2939.
10. 3) δ 15.2, 29.2, 40.4, 44.1, 91.7, 117.3, 128.3, 136.8, 166.9, 194.2.
11. Bergbreiter, D. E.; Weatherford, D. A. J. Chem. Soc., Chem. Commun. 1989, 883.
12. 3) δ 19.64, 23.20, 23.54, 25.08, 25.47, 27.75, 29.23, 30.71 (8xCH2), 40.08 (C-3a), 50.67 (OMe), 62.30 (C-14), 67.18 (C-20), 78.04 (C-7a), 98.80 (C-16), 107.50 (C-3), 123.21 (C-6), 134.51 (C-7), 166.54 (C-2), 172.02 (C=O).
13. ax as well as between H-3 and H-12 clearly establish the relative configuration of spiroketal carbon C-2.
14. For related palladium-catalyzed cascade reactions, see: a) Fugami, K.; Oshima, K.; Utimoto, K. Tetrahedron Lett. 1987, 28, 809. b) Larock, R. C.; Stinn, D. E. Tetrahedron Lett. 1989, 30, 2767. c) Frederickson, M.; Grigg, R.; Markandu, J.; Redpath, J. J. Chem. Soc., Chem. Commun. 1994, 2225. d) Sugiura, M.; Yanagisawa, M.; Nakai, T. Synlett 1995, 447.
15. For related palladium-catalyzed cascade reactions, see: a) Fugami, K.; Oshima, K.; Utimoto, K. Tetrahedron Lett. 1987, 28, 809. b) Larock, R. C.; Stinn, D. E. Tetrahedron Lett. 1989, 30, 2767. c) Frederickson, M.; Grigg, R.; Markandu, J.; Redpath, J. J. Chem. Soc., Chem. Commun. 1994, 2225. d) Sugiura, M.; Yanagisawa, M.; Nakai, T. Synlett 1995, 447.
16. For related palladium-catalyzed cascade reactions, see: a) Fugami, K.; Oshima, K.; Utimoto, K. Tetrahedron Lett. 1987, 28, 809. b) Larock, R. C.; Stinn, D. E. Tetrahedron Lett. 1989, 30, 2767. c) Frederickson, M.; Grigg, R.; Markandu, J.; Redpath, J. J. Chem. Soc., Chem. Commun. 1994, 2225. d) Sugiura, M.; Yanagisawa, M.; Nakai, T. Synlett 1995, 447.
17. For related palladium-catalyzed cascade reactions, see: a) Fugami, K.; Oshima, K.; Utimoto, K. Tetrahedron Lett. 1987, 28, 809. b) Larock, R. C.; Stinn, D. E. Tetrahedron Lett. 1989, 30, 2767. c) Frederickson, M.; Grigg, R.; Markandu, J.; Redpath, J. J. Chem. Soc., Chem. Commun. 1994, 2225. d) Sugiura, M.; Yanagisawa, M.; Nakai, T. Synlett 1995, 447.
18. 2Me) δ 2.99 (H-3, d, J = 7.5 Hz), 4.60 (m, H-7a); 11(inverted spiroketal, configuration of C-3 not determined) δ 3.27 (H-3, d. J = 8.2 Hz), 4.27 (m, H-7a).
19. Kupchan, S. M.; La Voie, E. J.; Branfman, A. R.; Fei, B. Y.; Bright, W. M.; Bryan, R. F. J. Am. Chem. Soc. 1977, 99, 3199.
20. Pettit, G. R.; Cragg, G. M.; Suffness, M. J. Org. Chem. 1985, 50, 5060 and references cited therein.