Practical synthesis of (±)-chlorovulone II

Journal of Organic Chemistry

Volumn 63, Issue 5, 1998, Pages 1668-1675

  Ciufolini, Marco A ^a   Zhu, Shuren ^a  

^a RICE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

4 CYCLOPENTENE 1,3 DIONE; CHLOROVULONE II; CLAVIRIDENONE D; PROSTANOID; UNCLASSIFIED DRUG;

ANTIINFLAMMATORY ACTIVITY; ANTINEOPLASTIC ACTIVITY; ARTICLE; CHEMICAL ANALYSIS; CHEMICAL MODIFICATION; CYCLIZATION; CYTOTOXICITY; DRUG ISOLATION; DRUG SYNTHESIS; PROSTAGLANDIN SYNTHESIS; STEREOCHEMISTRY;

EID: 0032489411     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo972073f     Document Type: Article

References (69)

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7. The absolute stereochemistry of these compounds was established by degradative and chiroptical techniques [(c) Kobayashi, M.; Yasuzawa, T.; Yoshihara, M.; Son, B. W.; Kyogoku, Y.; Kitagawa, I. Chem. Pharm. Bull. 1983, 31, 1440. (d) Kikuchi, H.; Tsukitani, Y.; Iguchi, K.; Yamada, Y. Tetrahedron Lett. 1983, 24, 1549] and confirmed by synthesis. (e) Hashimoto, S.; Arai, Y.; Hamanaka, N. Tetrahedron Lett. 1985, 26, 2679. (f) Corey, E. J.; Mehrotra, M. M. J. Am. Chem. Soc. 1984, 106, 3384. (g) Nagaoka, H.; Miyakoshi, T.; Yamada, Y. Tetrahedron Lett. 1984, 25, 3621. (h) Shibasaki, N.; Ogawa, Y. Tetrahedron Lett. 1985, 26, 3841. (i) Zhu, J.; Yang, J. Y.; Klunder, A. J. H.; Liu, Z. Y.; Zwanenburg, B. Tetrahedron 1995, 51, 5847. (j) Takeda, K.; Nakajima, A.; Yoshii, E. Synlett 1997, 255.
8. The absolute stereochemistry of these compounds was established by degradative and chiroptical techniques [(c) Kobayashi, M.; Yasuzawa, T.; Yoshihara, M.; Son, B. W.; Kyogoku, Y.; Kitagawa, I. Chem. Pharm. Bull. 1983, 31, 1440. (d) Kikuchi, H.; Tsukitani, Y.; Iguchi, K.; Yamada, Y. Tetrahedron Lett. 1983, 24, 1549] and confirmed by synthesis. (e) Hashimoto, S.; Arai, Y.; Hamanaka, N. Tetrahedron Lett. 1985, 26, 2679. (f) Corey, E. J.; Mehrotra, M. M. J. Am. Chem. Soc. 1984, 106, 3384. (g) Nagaoka, H.; Miyakoshi, T.; Yamada, Y. Tetrahedron Lett. 1984, 25, 3621. (h) Shibasaki, N.; Ogawa, Y. Tetrahedron Lett. 1985, 26, 3841. (i) Zhu, J.; Yang, J. Y.; Klunder, A. J. H.; Liu, Z. Y.; Zwanenburg, B. Tetrahedron 1995, 51, 5847. (j) Takeda, K.; Nakajima, A.; Yoshii, E. Synlett 1997, 255.
9. The absolute stereochemistry of these compounds was established by degradative and chiroptical techniques [(c) Kobayashi, M.; Yasuzawa, T.; Yoshihara, M.; Son, B. W.; Kyogoku, Y.; Kitagawa, I. Chem. Pharm. Bull. 1983, 31, 1440. (d) Kikuchi, H.; Tsukitani, Y.; Iguchi, K.; Yamada, Y. Tetrahedron Lett. 1983, 24, 1549] and confirmed by synthesis. (e) Hashimoto, S.; Arai, Y.; Hamanaka, N. Tetrahedron Lett. 1985, 26, 2679. (f) Corey, E. J.; Mehrotra, M. M. J. Am. Chem. Soc. 1984, 106, 3384. (g) Nagaoka, H.; Miyakoshi, T.; Yamada, Y. Tetrahedron Lett. 1984, 25, 3621. (h) Shibasaki, N.; Ogawa, Y. Tetrahedron Lett. 1985, 26, 3841. (i) Zhu, J.; Yang, J. Y.; Klunder, A. J. H.; Liu, Z. Y.; Zwanenburg, B. Tetrahedron 1995, 51, 5847. (j) Takeda, K.; Nakajima, A.; Yoshii, E. Synlett 1997, 255.
10. The absolute stereochemistry of these compounds was established by degradative and chiroptical techniques [(c) Kobayashi, M.; Yasuzawa, T.; Yoshihara, M.; Son, B. W.; Kyogoku, Y.; Kitagawa, I. Chem. Pharm. Bull. 1983, 31, 1440. (d) Kikuchi, H.; Tsukitani, Y.; Iguchi, K.; Yamada, Y. Tetrahedron Lett. 1983, 24, 1549] and confirmed by synthesis. (e) Hashimoto, S.; Arai, Y.; Hamanaka, N. Tetrahedron Lett. 1985, 26, 2679. (f) Corey, E. J.; Mehrotra, M. M. J. Am. Chem. Soc. 1984, 106, 3384. (g) Nagaoka, H.; Miyakoshi, T.; Yamada, Y. Tetrahedron Lett. 1984, 25, 3621. (h) Shibasaki, N.; Ogawa, Y. Tetrahedron Lett. 1985, 26, 3841. (i) Zhu, J.; Yang, J. Y.; Klunder, A. J. H.; Liu, Z. Y.; Zwanenburg, B. Tetrahedron 1995, 51, 5847. (j) Takeda, K.; Nakajima, A.; Yoshii, E. Synlett 1997, 255.
11. The absolute stereochemistry of these compounds was established by degradative and chiroptical techniques [(c) Kobayashi, M.; Yasuzawa, T.; Yoshihara, M.; Son, B. W.; Kyogoku, Y.; Kitagawa, I. Chem. Pharm. Bull. 1983, 31, 1440. (d) Kikuchi, H.; Tsukitani, Y.; Iguchi, K.; Yamada, Y. Tetrahedron Lett. 1983, 24, 1549] and confirmed by synthesis. (e) Hashimoto, S.; Arai, Y.; Hamanaka, N. Tetrahedron Lett. 1985, 26, 2679. (f) Corey, E. J.; Mehrotra, M. M. J. Am. Chem. Soc. 1984, 106, 3384. (g) Nagaoka, H.; Miyakoshi, T.; Yamada, Y. Tetrahedron Lett. 1984, 25, 3621. (h) Shibasaki, N.; Ogawa, Y. Tetrahedron Lett. 1985, 26, 3841. (i) Zhu, J.; Yang, J. Y.; Klunder, A. J. H.; Liu, Z. Y.; Zwanenburg, B. Tetrahedron 1995, 51, 5847. (j) Takeda, K.; Nakajima, A.; Yoshii, E. Synlett 1997, 255.
12. The absolute stereochemistry of these compounds was established by degradative and chiroptical techniques [(c) Kobayashi, M.; Yasuzawa, T.; Yoshihara, M.; Son, B. W.; Kyogoku, Y.; Kitagawa, I. Chem. Pharm. Bull. 1983, 31, 1440. (d) Kikuchi, H.; Tsukitani, Y.; Iguchi, K.; Yamada, Y. Tetrahedron Lett. 1983, 24, 1549] and confirmed by synthesis. (e) Hashimoto, S.; Arai, Y.; Hamanaka, N. Tetrahedron Lett. 1985, 26, 2679. (f) Corey, E. J.; Mehrotra, M. M. J. Am. Chem. Soc. 1984, 106, 3384. (g) Nagaoka, H.; Miyakoshi, T.; Yamada, Y. Tetrahedron Lett. 1984, 25, 3621. (h) Shibasaki, N.; Ogawa, Y. Tetrahedron Lett. 1985, 26, 3841. (i) Zhu, J.; Yang, J. Y.; Klunder, A. J. H.; Liu, Z. Y.; Zwanenburg, B. Tetrahedron 1995, 51, 5847. (j) Takeda, K.; Nakajima, A.; Yoshii, E. Synlett 1997, 255.
13. The absolute stereochemistry of these compounds was established by degradative and chiroptical techniques [(c) Kobayashi, M.; Yasuzawa, T.; Yoshihara, M.; Son, B. W.; Kyogoku, Y.; Kitagawa, I. Chem. Pharm. Bull. 1983, 31, 1440. (d) Kikuchi, H.; Tsukitani, Y.; Iguchi, K.; Yamada, Y. Tetrahedron Lett. 1983, 24, 1549] and confirmed by synthesis. (e) Hashimoto, S.; Arai, Y.; Hamanaka, N. Tetrahedron Lett. 1985, 26, 2679. (f) Corey, E. J.; Mehrotra, M. M. J. Am. Chem. Soc. 1984, 106, 3384. (g) Nagaoka, H.; Miyakoshi, T.; Yamada, Y. Tetrahedron Lett. 1984, 25, 3621. (h) Shibasaki, N.; Ogawa, Y. Tetrahedron Lett. 1985, 26, 3841. (i) Zhu, J.; Yang, J. Y.; Klunder, A. J. H.; Liu, Z. Y.; Zwanenburg, B. Tetrahedron 1995, 51, 5847. (j) Takeda, K.; Nakajima, A.; Yoshii, E. Synlett 1997, 255.
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40. 2O in pyridine gave the monoacetate in 50% Chromatographied yield, plus diacetate (25%) and unreacted starting diol (25%).
41. A catalyst for enantioselective ene-like reactions similar to ours has been described by: Carreira, E.; Lee, W.; Singer, R. A. J. Am. Chem. Soc. 1995, 117, 3649. The Carreira catalyst is reported to produce excellent results with ynals, but not with enals. By contrast, our catalytic system works well with enals, but ynals are less successful.
42. This ene product was obtained in 80% yield, but it was contaminated with small amounts of byproducts of unknown structure. Purification to homogeineity was difficult.
43. The stereochemistry of 26-27 was assigned on the basis of cyclic acetonide formation as described in: Ciufolini, M. A.; Zhu, S. Tetrahedron Lett. 1997, 38, in press.
44. Cf., e.g.: (a) Morikawa, T.; Washio, Y.; Harada, S.; Hanai, R.; Kayashita, T.; Nemoto, H.; Shiro, M.; Taguchi, T. J. Chem. Soc., Perkin Trans. 1 1995, 271. (b) Lesueur, C.; Nauguier, R.; Bertrand, M. P.; Hoffmann, P.; DeMesmaecker, A. D. Tetrahedron 1994, 50, 767. (c) Curran, D. P.; Sun, S. Tetrahedron Lett. 1993, 34, 6181 and references cited therein. See also ref 19, pp 935 ff.
45. Cf., e.g.: (a) Morikawa, T.; Washio, Y.; Harada, S.; Hanai, R.; Kayashita, T.; Nemoto, H.; Shiro, M.; Taguchi, T. J. Chem. Soc., Perkin Trans. 1 1995, 271. (b) Lesueur, C.; Nauguier, R.; Bertrand, M. P.; Hoffmann, P.; DeMesmaecker, A. D. Tetrahedron 1994, 50, 767. (c) Curran, D. P.; Sun, S. Tetrahedron Lett. 1993, 34, 6181 and references cited therein. See also ref 19, pp 935 ff.
46. Cf., e.g.: (a) Morikawa, T.; Washio, Y.; Harada, S.; Hanai, R.; Kayashita, T.; Nemoto, H.; Shiro, M.; Taguchi, T. J. Chem. Soc., Perkin Trans. 1 1995, 271. (b) Lesueur, C.; Nauguier, R.; Bertrand, M. P.; Hoffmann, P.; DeMesmaecker, A. D. Tetrahedron 1994, 50, 767. (c) Curran, D. P.; Sun, S. Tetrahedron Lett. 1993, 34, 6181 and references cited therein. See also ref 19, pp 935 ff.
47. For a detailed discussion of the Felkin-Anh model, see: Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; John Wiley & Sons: New York, 1994; pp 875-880.
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51. Calculation were carried out with the Hyperchem 4.0 package, available from Hypercube, Inc., Ontario, Canada.
52. Recall that an Si-O bond is rather long compared to a C-O bond: approximately 1.64 Å vs 1.43 A. Because steric interactions are inversely dependent on the 6th power of the distance between groups, the steric interactions between the silyl subunit and the rest of the molecule are not as severe as those created by an MIP unit.
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59. Cf. (a) Lu, H.-J.; Llinas-Brunet, M. Can. J. Chem. 1984, 62, 1747. (b) Cardinale, G.; Laan, J. A. M.; Ward, J. P. Reel. Trav. Chim. Pays-Bas 1987, 106, 62. (c) Paquette, L. A.; Vannucci, C.; Rogers, R. D. J. Am. Chem. Soc. 1989, 111, 5792. (d) Houwen-Claassen, A. A. M.; Klunder, A. J. H.; Kooy, M. G; Steffann, J.; Zwanenburg, B. Tetrahedron 1989, 45, 7109.
60. Cf. (a) Lu, H.-J.; Llinas-Brunet, M. Can. J. Chem. 1984, 62, 1747. (b) Cardinale, G.; Laan, J. A. M.; Ward, J. P. Reel. Trav. Chim. Pays-Bas 1987, 106, 62. (c) Paquette, L. A.; Vannucci, C.; Rogers, R. D. J. Am. Chem. Soc. 1989, 111, 5792. (d) Houwen-Claassen, A. A. M.; Klunder, A. J. H.; Kooy, M. G; Steffann, J.; Zwanenburg, B. Tetrahedron 1989, 45, 7109.
61. Cf. (a) Lu, H.-J.; Llinas-Brunet, M. Can. J. Chem. 1984, 62, 1747. (b) Cardinale, G.; Laan, J. A. M.; Ward, J. P. Reel. Trav. Chim. Pays-Bas 1987, 106, 62. (c) Paquette, L. A.; Vannucci, C.; Rogers, R. D. J. Am. Chem. Soc. 1989, 111, 5792. (d) Houwen-Claassen, A. A. M.; Klunder, A. J. H.; Kooy, M. G; Steffann, J.; Zwanenburg, B. Tetrahedron 1989, 45, 7109.
62. Cf. Lepitskaya, M. A.; Manukina, T. A.; Pivnitskii, K. K. Zh. Org. Khim. 1986, 22, 872.
63. Cf. Takahashi, K.; Namekata, N.; Takase, K.; Takeuchi, A. Tetrahedron Lett. 1987, 28, 5683.
64. Luche, J. L. J. Am. Chem. Soc. 1978, 100, 2226.
65. For a review of the Wittig reaction see: Schlosser, M. Top. Stereochem. 1970, 5, 1.
66. Corey, E. J.; Schmidt, G. Tetrahedron Lett. 1979, 20, 399.
67. Reference 8 describes a route to 53 that involves three steps from δ-valerolactone: (i) methanolysis, (ii) Swern oxidation of the hydroxy ester, and (iii) Wittig reaction. A more practical two-step alternative involving a Schreiber ozonolysis (Claus, R. E., Schreiber, S. L. Organic Syntheses; Wiley: New York, 1990; Collect. Vol. VII, p 168, Schreiber, S. L.; Claus, R. E.; Regan, J. Tetrahedron Lett. 1982, 23, 3867) is detailed in the Experimental Section.
68. Reference 8 describes a route to 53 that involves three steps from δ-valerolactone: (i) methanolysis, (ii) Swern oxidation of the hydroxy ester, and (iii) Wittig reaction. A more practical two-step alternative involving a Schreiber ozonolysis (Claus, R. E., Schreiber, S. L. Organic Syntheses; Wiley: New York, 1990; Collect. Vol. VII, p 168, Schreiber, S. L.; Claus, R. E.; Regan, J. Tetrahedron Lett. 1982, 23, 3867) is detailed in the Experimental Section.
69. 2CO.