Highly stereocontrolled formal synthesis of brassinolide via chiral sulfoxide-directed SN2′ reactions

Journal of Organic Chemistry

Volumn 61, Issue 1, 1996, Pages 109-117

  Marino, Joseph P ^a   De Dios, Alfonso ^a   Anna, Laura J ^a   Fernández De La Pradilla, Roberto ^a,b  

^a UNIVERSITY OF MICHIGAN   (United States)

^b INSTITUTO DE QUÍMICA ORGÁNICA GENERAL   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000637513     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo951264k     Document Type: Article

References (81)

1. Grove, M. D.; Spencer, G. F.; Rohwedder, W. K.; Mandava, N.; Worley, J. F.; Warthen, J. D.; Steffens, G. L.; Flippen-Anderson, J. L.; Cook, J. C., Jr. Nature 1979, 281, 216-217.
2. Brassinosteroids, Chemistry, Bioactivity and Applications; Cutler, H. G., Yokota, T., Adam, G., Eds.; ACS Symposium Series 474; American Chemical Society: Washington DC, 1991: (a) Natural occurrences: Kim, S.-K., Chapter 3. (b) Improvements in elongation, yields and resistance of various crops, inter alia: Schilling, G.; Schiller, C.; Otto, S., Chapter 18; He, R.; Wang, G.; Wang, X., Chapter 19; Sasse, J. M., Chapter 22. (c) Antitumoral activity: Bach, T. J.; Roth, P. S.; Thompson, M. J., Chapter 15. (d) Isolation: Steffens, G. L., Chapter 1. (e) Synthesis: McMorris, T. C.; Donaubauer, J R.; Silveira, M. H.; Molinski, T. F., Chapter 4. (f) Biological activity of naturally occurring 24-epibrassinolide: Ikekawa, N.; Zhao, Y.-J., Chapter 24.
3. Brassinosteroids, Chemistry, Bioactivity and Applications; Cutler, H. G., Yokota, T., Adam, G., Eds.; ACS Symposium Series 474; American Chemical Society: Washington DC, 1991: (a) Natural occurrences: Kim, S.-K., Chapter 3. (b) Improvements in elongation, yields and resistance of various crops, inter alia: Schilling, G.; Schiller, C.; Otto, S., Chapter 18; He, R.; Wang, G.; Wang, X., Chapter 19; Sasse, J. M., Chapter 22. (c) Antitumoral activity: Bach, T. J.; Roth, P. S.; Thompson, M. J., Chapter 15. (d) Isolation: Steffens, G. L., Chapter 1. (e) Synthesis: McMorris, T. C.; Donaubauer, J R.; Silveira, M. H.; Molinski, T. F., Chapter 4. (f) Biological activity of naturally occurring 24-epibrassinolide: Ikekawa, N.; Zhao, Y.-J., Chapter 24.
4. Brassinosteroids, Chemistry, Bioactivity and Applications; Cutler, H. G., Yokota, T., Adam, G., Eds.; ACS Symposium Series 474; American Chemical Society: Washington DC, 1991: (a) Natural occurrences: Kim, S.-K., Chapter 3. (b) Improvements in elongation, yields and resistance of various crops, inter alia: Schilling, G.; Schiller, C.; Otto, S., Chapter 18; He, R.; Wang, G.; Wang, X., Chapter 19; Sasse, J. M., Chapter 22. (c) Antitumoral activity: Bach, T. J.; Roth, P. S.; Thompson, M. J., Chapter 15. (d) Isolation: Steffens, G. L., Chapter 1. (e) Synthesis: McMorris, T. C.; Donaubauer, J R.; Silveira, M. H.; Molinski, T. F., Chapter 4. (f) Biological activity of naturally occurring 24-epibrassinolide: Ikekawa, N.; Zhao, Y.-J., Chapter 24.
5. Brassinosteroids, Chemistry, Bioactivity and Applications; Cutler, H. G., Yokota, T., Adam, G., Eds.; ACS Symposium Series 474; American Chemical Society: Washington DC, 1991: (a) Natural occurrences: Kim, S.-K., Chapter 3. (b) Improvements in elongation, yields and resistance of various crops, inter alia: Schilling, G.; Schiller, C.; Otto, S., Chapter 18; He, R.; Wang, G.; Wang, X., Chapter 19; Sasse, J. M., Chapter 22. (c) Antitumoral activity: Bach, T. J.; Roth, P. S.; Thompson, M. J., Chapter 15. (d) Isolation: Steffens, G. L., Chapter 1. (e) Synthesis: McMorris, T. C.; Donaubauer, J R.; Silveira, M. H.; Molinski, T. F., Chapter 4. (f) Biological activity of naturally occurring 24-epibrassinolide: Ikekawa, N.; Zhao, Y.-J., Chapter 24.
6. Brassinosteroids, Chemistry, Bioactivity and Applications; Cutler, H. G., Yokota, T., Adam, G., Eds.; ACS Symposium Series 474; American Chemical Society: Washington DC, 1991: (a) Natural occurrences: Kim, S.-K., Chapter 3. (b) Improvements in elongation, yields and resistance of various crops, inter alia: Schilling, G.; Schiller, C.; Otto, S., Chapter 18; He, R.; Wang, G.; Wang, X., Chapter 19; Sasse, J. M., Chapter 22. (c) Antitumoral activity: Bach, T. J.; Roth, P. S.; Thompson, M. J., Chapter 15. (d) Isolation: Steffens, G. L., Chapter 1. (e) Synthesis: McMorris, T. C.; Donaubauer, J R.; Silveira, M. H.; Molinski, T. F., Chapter 4. (f) Biological activity of naturally occurring 24-epibrassinolide: Ikekawa, N.; Zhao, Y.-J., Chapter 24.
7. Brassinosteroids, Chemistry, Bioactivity and Applications; Cutler, H. G., Yokota, T., Adam, G., Eds.; ACS Symposium Series 474; American Chemical Society: Washington DC, 1991: (a) Natural occurrences: Kim, S.-K., Chapter 3. (b) Improvements in elongation, yields and resistance of various crops, inter alia: Schilling, G.; Schiller, C.; Otto, S., Chapter 18; He, R.; Wang, G.; Wang, X., Chapter 19; Sasse, J. M., Chapter 22. (c) Antitumoral activity: Bach, T. J.; Roth, P. S.; Thompson, M. J., Chapter 15. (d) Isolation: Steffens, G. L., Chapter 1. (e) Synthesis: McMorris, T. C.; Donaubauer, J R.; Silveira, M. H.; Molinski, T. F., Chapter 4. (f) Biological activity of naturally occurring 24-epibrassinolide: Ikekawa, N.; Zhao, Y.-J., Chapter 24.
8. Brassinosteroids, Chemistry, Bioactivity and Applications; Cutler, H. G., Yokota, T., Adam, G., Eds.; ACS Symposium Series 474; American Chemical Society: Washington DC, 1991: (a) Natural occurrences: Kim, S.-K., Chapter 3. (b) Improvements in elongation, yields and resistance of various crops, inter alia: Schilling, G.; Schiller, C.; Otto, S., Chapter 18; He, R.; Wang, G.; Wang, X., Chapter 19; Sasse, J. M., Chapter 22. (c) Antitumoral activity: Bach, T. J.; Roth, P. S.; Thompson, M. J., Chapter 15. (d) Isolation: Steffens, G. L., Chapter 1. (e) Synthesis: McMorris, T. C.; Donaubauer, J R.; Silveira, M. H.; Molinski, T. F., Chapter 4. (f) Biological activity of naturally occurring 24-epibrassinolide: Ikekawa, N.; Zhao, Y.-J., Chapter 24.
9. For accounts on this topic, see: (a) Zhou, W.-S. Pure Appl. Chem. 1989, 61, 431-434. (b) Khripach, V. A. Pure Appl. Chem. 1990, 62, 1319-1324.
10. For accounts on this topic, see: (a) Zhou, W.-S. Pure Appl. Chem. 1989, 61, 431-434. (b) Khripach, V. A. Pure Appl. Chem. 1990, 62, 1319-1324.
11. For some leading examples, see: (a) Ishiguro, M.; Takatsuto, S.; Morisaki, M.; Ikekawa, N. J. Chem. Soc., Chem. Commun. 1980, 962-964. (b) Fung, S.; Siddall, J. B. J. Am. Chem. Soc. 1980, 102, 6580-6581. (c) Hayami, H.; Sato, M.; Kanemoto, S.; Morizawa, Y.; Oshima, K.; Nozaki, H. J. Am. Chem. Soc. 1983, 105, 4491-4492. (d) Sakakibara, M.; Mori, K. Agric. Biol. Chem. 1983, 47, 663-664. (e) Mori, K.; Sakakibara, M.; Okada, K. Tetrahedron 1984, 40, 1767-1781. (f) Takahashi, T.; Ootake, A.; Yamada, H.; Tsuji, J. Tetrahedron Lett. 1985, 26, 69-72. (g) Aburatani, M.; Takeuchi, T.; Mori, K. Agric. Biol. Chem. 1986, 50, 3043-3047. (h) Shen, Z.-W.; Zhou, W -S. J. Chem. Soc., Perkin Trans. 1 1990, 1765-1767. (i) Back, T. G.; Krishna, M. V. J. Org. Chem. 1991, 56, 454-457. (j) Zhou, W.-S.; Jiang, B.; Pan, X.-F. Tetrahedron 1992, 48, 1837-1852. (k) Back, T. G.; Blazecka, P. G., Krishna, M. V. Can. J. Chem. 1993, 71, 156-163. (l) Hazra, B. G.; Joshi, P. L.; Bahule, B. B.; Argade, N. P.; Pore, V. S.; Chordia, M. D. Tetrahedron 1994, 50, 2523-2532. See also ref 31.
12. For some leading examples, see: (a) Ishiguro, M.; Takatsuto, S.; Morisaki, M.; Ikekawa, N. J. Chem. Soc., Chem. Commun. 1980, 962-964. (b) Fung, S.; Siddall, J. B. J. Am. Chem. Soc. 1980, 102, 6580-6581. (c) Hayami, H.; Sato, M.; Kanemoto, S.; Morizawa, Y.; Oshima, K.; Nozaki, H. J. Am. Chem. Soc. 1983, 105, 4491-4492. (d) Sakakibara, M.; Mori, K. Agric. Biol. Chem. 1983, 47, 663-664. (e) Mori, K.; Sakakibara, M.; Okada, K. Tetrahedron 1984, 40, 1767-1781. (f) Takahashi, T.; Ootake, A.; Yamada, H.; Tsuji, J. Tetrahedron Lett. 1985, 26, 69-72. (g) Aburatani, M.; Takeuchi, T.; Mori, K. Agric. Biol. Chem. 1986, 50, 3043-3047. (h) Shen, Z.-W.; Zhou, W -S. J. Chem. Soc., Perkin Trans. 1 1990, 1765-1767. (i) Back, T. G.; Krishna, M. V. J. Org. Chem. 1991, 56, 454-457. (j) Zhou, W.-S.; Jiang, B.; Pan, X.-F. Tetrahedron 1992, 48, 1837-1852. (k) Back, T. G.; Blazecka, P. G., Krishna, M. V. Can. J. Chem. 1993, 71, 156-163. (l) Hazra, B. G.; Joshi, P. L.; Bahule, B. B.; Argade, N. P.; Pore, V. S.; Chordia, M. D. Tetrahedron 1994, 50, 2523-2532. See also ref 31.
13. For some leading examples, see: (a) Ishiguro, M.; Takatsuto, S.; Morisaki, M.; Ikekawa, N. J. Chem. Soc., Chem. Commun. 1980, 962-964. (b) Fung, S.; Siddall, J. B. J. Am. Chem. Soc. 1980, 102, 6580-6581. (c) Hayami, H.; Sato, M.; Kanemoto, S.; Morizawa, Y.; Oshima, K.; Nozaki, H. J. Am. Chem. Soc. 1983, 105, 4491-4492. (d) Sakakibara, M.; Mori, K. Agric. Biol. Chem. 1983, 47, 663-664. (e) Mori, K.; Sakakibara, M.; Okada, K. Tetrahedron 1984, 40, 1767-1781. (f) Takahashi, T.; Ootake, A.; Yamada, H.; Tsuji, J. Tetrahedron Lett. 1985, 26, 69-72. (g) Aburatani, M.; Takeuchi, T.; Mori, K. Agric. Biol. Chem. 1986, 50, 3043-3047. (h) Shen, Z.-W.; Zhou, W -S. J. Chem. Soc., Perkin Trans. 1 1990, 1765-1767. (i) Back, T. G.; Krishna, M. V. J. Org. Chem. 1991, 56, 454-457. (j) Zhou, W.-S.; Jiang, B.; Pan, X.-F. Tetrahedron 1992, 48, 1837-1852. (k) Back, T. G.; Blazecka, P. G., Krishna, M. V. Can. J. Chem. 1993, 71, 156-163. (l) Hazra, B. G.; Joshi, P. L.; Bahule, B. B.; Argade, N. P.; Pore, V. S.; Chordia, M. D. Tetrahedron 1994, 50, 2523-2532. See also ref 31.
14. For some leading examples, see: (a) Ishiguro, M.; Takatsuto, S.; Morisaki, M.; Ikekawa, N. J. Chem. Soc., Chem. Commun. 1980, 962-964. (b) Fung, S.; Siddall, J. B. J. Am. Chem. Soc. 1980, 102, 6580-6581. (c) Hayami, H.; Sato, M.; Kanemoto, S.; Morizawa, Y.; Oshima, K.; Nozaki, H. J. Am. Chem. Soc. 1983, 105, 4491-4492. (d) Sakakibara, M.; Mori, K. Agric. Biol. Chem. 1983, 47, 663-664. (e) Mori, K.; Sakakibara, M.; Okada, K. Tetrahedron 1984, 40, 1767-1781. (f) Takahashi, T.; Ootake, A.; Yamada, H.; Tsuji, J. Tetrahedron Lett. 1985, 26, 69-72. (g) Aburatani, M.; Takeuchi, T.; Mori, K. Agric. Biol. Chem. 1986, 50, 3043-3047. (h) Shen, Z.-W.; Zhou, W -S. J. Chem. Soc., Perkin Trans. 1 1990, 1765-1767. (i) Back, T. G.; Krishna, M. V. J. Org. Chem. 1991, 56, 454-457. (j) Zhou, W.-S.; Jiang, B.; Pan, X.-F. Tetrahedron 1992, 48, 1837-1852. (k) Back, T. G.; Blazecka, P. G., Krishna, M. V. Can. J. Chem. 1993, 71, 156-163. (l) Hazra, B. G.; Joshi, P. L.; Bahule, B. B.; Argade, N. P.; Pore, V. S.; Chordia, M. D. Tetrahedron 1994, 50, 2523-2532. See also ref 31.
15. For some leading examples, see: (a) Ishiguro, M.; Takatsuto, S.; Morisaki, M.; Ikekawa, N. J. Chem. Soc., Chem. Commun. 1980, 962-964. (b) Fung, S.; Siddall, J. B. J. Am. Chem. Soc. 1980, 102, 6580-6581. (c) Hayami, H.; Sato, M.; Kanemoto, S.; Morizawa, Y.; Oshima, K.; Nozaki, H. J. Am. Chem. Soc. 1983, 105, 4491-4492. (d) Sakakibara, M.; Mori, K. Agric. Biol. Chem. 1983, 47, 663-664. (e) Mori, K.; Sakakibara, M.; Okada, K. Tetrahedron 1984, 40, 1767-1781. (f) Takahashi, T.; Ootake, A.; Yamada, H.; Tsuji, J. Tetrahedron Lett. 1985, 26, 69-72. (g) Aburatani, M.; Takeuchi, T.; Mori, K. Agric. Biol. Chem. 1986, 50, 3043-3047. (h) Shen, Z.-W.; Zhou, W -S. J. Chem. Soc., Perkin Trans. 1 1990, 1765-1767. (i) Back, T. G.; Krishna, M. V. J. Org. Chem. 1991, 56, 454-457. (j) Zhou, W.-S.; Jiang, B.; Pan, X.-F. Tetrahedron 1992, 48, 1837-1852. (k) Back, T. G.; Blazecka, P. G., Krishna, M. V. Can. J. Chem. 1993, 71, 156-163. (l) Hazra, B. G.; Joshi, P. L.; Bahule, B. B.; Argade, N. P.; Pore, V. S.; Chordia, M. D. Tetrahedron 1994, 50, 2523-2532. See also ref 31.
16. For some leading examples, see: (a) Ishiguro, M.; Takatsuto, S.; Morisaki, M.; Ikekawa, N. J. Chem. Soc., Chem. Commun. 1980, 962-964. (b) Fung, S.; Siddall, J. B. J. Am. Chem. Soc. 1980, 102, 6580-6581. (c) Hayami, H.; Sato, M.; Kanemoto, S.; Morizawa, Y.; Oshima, K.; Nozaki, H. J. Am. Chem. Soc. 1983, 105, 4491-4492. (d) Sakakibara, M.; Mori, K. Agric. Biol. Chem. 1983, 47, 663-664. (e) Mori, K.; Sakakibara, M.; Okada, K. Tetrahedron 1984, 40, 1767-1781. (f) Takahashi, T.; Ootake, A.; Yamada, H.; Tsuji, J. Tetrahedron Lett. 1985, 26, 69-72. (g) Aburatani, M.; Takeuchi, T.; Mori, K. Agric. Biol. Chem. 1986, 50, 3043-3047. (h) Shen, Z.-W.; Zhou, W -S. J. Chem. Soc., Perkin Trans. 1 1990, 1765-1767. (i) Back, T. G.; Krishna, M. V. J. Org. Chem. 1991, 56, 454-457. (j) Zhou, W.-S.; Jiang, B.; Pan, X.-F. Tetrahedron 1992, 48, 1837-1852. (k) Back, T. G.; Blazecka, P. G., Krishna, M. V. Can. J. Chem. 1993, 71, 156-163. (l) Hazra, B. G.; Joshi, P. L.; Bahule, B. B.; Argade, N. P.; Pore, V. S.; Chordia, M. D. Tetrahedron 1994, 50, 2523-2532. See also ref 31.
17. For some leading examples, see: (a) Ishiguro, M.; Takatsuto, S.; Morisaki, M.; Ikekawa, N. J. Chem. Soc., Chem. Commun. 1980, 962-964. (b) Fung, S.; Siddall, J. B. J. Am. Chem. Soc. 1980, 102, 6580-6581. (c) Hayami, H.; Sato, M.; Kanemoto, S.; Morizawa, Y.; Oshima, K.; Nozaki, H. J. Am. Chem. Soc. 1983, 105, 4491-4492. (d) Sakakibara, M.; Mori, K. Agric. Biol. Chem. 1983, 47, 663-664. (e) Mori, K.; Sakakibara, M.; Okada, K. Tetrahedron 1984, 40, 1767-1781. (f) Takahashi, T.; Ootake, A.; Yamada, H.; Tsuji, J. Tetrahedron Lett. 1985, 26, 69-72. (g) Aburatani, M.; Takeuchi, T.; Mori, K. Agric. Biol. Chem. 1986, 50, 3043-3047. (h) Shen, Z.-W.; Zhou, W -S. J. Chem. Soc., Perkin Trans. 1 1990, 1765-1767. (i) Back, T. G.; Krishna, M. V. J. Org. Chem. 1991, 56, 454-457. (j) Zhou, W.-S.; Jiang, B.; Pan, X.-F. Tetrahedron 1992, 48, 1837-1852. (k) Back, T. G.; Blazecka, P. G., Krishna, M. V. Can. J. Chem. 1993, 71, 156-163. (l) Hazra, B. G.; Joshi, P. L.; Bahule, B. B.; Argade, N. P.; Pore, V. S.; Chordia, M. D. Tetrahedron 1994, 50, 2523-2532. See also ref 31.
18. For some leading examples, see: (a) Ishiguro, M.; Takatsuto, S.; Morisaki, M.; Ikekawa, N. J. Chem. Soc., Chem. Commun. 1980, 962-964. (b) Fung, S.; Siddall, J. B. J. Am. Chem. Soc. 1980, 102, 6580-6581. (c) Hayami, H.; Sato, M.; Kanemoto, S.; Morizawa, Y.; Oshima, K.; Nozaki, H. J. Am. Chem. Soc. 1983, 105, 4491-4492. (d) Sakakibara, M.; Mori, K. Agric. Biol. Chem. 1983, 47, 663-664. (e) Mori, K.; Sakakibara, M.; Okada, K. Tetrahedron 1984, 40, 1767-1781. (f) Takahashi, T.; Ootake, A.; Yamada, H.; Tsuji, J. Tetrahedron Lett. 1985, 26, 69-72. (g) Aburatani, M.; Takeuchi, T.; Mori, K. Agric. Biol. Chem. 1986, 50, 3043-3047. (h) Shen, Z.-W.; Zhou, W -S. J. Chem. Soc., Perkin Trans. 1 1990, 1765-1767. (i) Back, T. G.; Krishna, M. V. J. Org. Chem. 1991, 56, 454-457. (j) Zhou, W.-S.; Jiang, B.; Pan, X.-F. Tetrahedron 1992, 48, 1837-1852. (k) Back, T. G.; Blazecka, P. G., Krishna, M. V. Can. J. Chem. 1993, 71, 156-163. (l) Hazra, B. G.; Joshi, P. L.; Bahule, B. B.; Argade, N. P.; Pore, V. S.; Chordia, M. D. Tetrahedron 1994, 50, 2523-2532. See also ref 31.
19. For some leading examples, see: (a) Ishiguro, M.; Takatsuto, S.; Morisaki, M.; Ikekawa, N. J. Chem. Soc., Chem. Commun. 1980, 962-964. (b) Fung, S.; Siddall, J. B. J. Am. Chem. Soc. 1980, 102, 6580-6581. (c) Hayami, H.; Sato, M.; Kanemoto, S.; Morizawa, Y.; Oshima, K.; Nozaki, H. J. Am. Chem. Soc. 1983, 105, 4491-4492. (d) Sakakibara, M.; Mori, K. Agric. Biol. Chem. 1983, 47, 663-664. (e) Mori, K.; Sakakibara, M.; Okada, K. Tetrahedron 1984, 40, 1767-1781. (f) Takahashi, T.; Ootake, A.; Yamada, H.; Tsuji, J. Tetrahedron Lett. 1985, 26, 69-72. (g) Aburatani, M.; Takeuchi, T.; Mori, K. Agric. Biol. Chem. 1986, 50, 3043-3047. (h) Shen, Z.-W.; Zhou, W -S. J. Chem. Soc., Perkin Trans. 1 1990, 1765-1767. (i) Back, T. G.; Krishna, M. V. J. Org. Chem. 1991, 56, 454-457. (j) Zhou, W.-S.; Jiang, B.; Pan, X.-F. Tetrahedron 1992, 48, 1837-1852. (k) Back, T. G.; Blazecka, P. G., Krishna, M. V. Can. J. Chem. 1993, 71, 156-163. (l) Hazra, B. G.; Joshi, P. L.; Bahule, B. B.; Argade, N. P.; Pore, V. S.; Chordia, M. D. Tetrahedron 1994, 50, 2523-2532. See also ref 31.
20. For some leading examples, see: (a) Ishiguro, M.; Takatsuto, S.; Morisaki, M.; Ikekawa, N. J. Chem. Soc., Chem. Commun. 1980, 962-964. (b) Fung, S.; Siddall, J. B. J. Am. Chem. Soc. 1980, 102, 6580-6581. (c) Hayami, H.; Sato, M.; Kanemoto, S.; Morizawa, Y.; Oshima, K.; Nozaki, H. J. Am. Chem. Soc. 1983, 105, 4491-4492. (d) Sakakibara, M.; Mori, K. Agric. Biol. Chem. 1983, 47, 663-664. (e) Mori, K.; Sakakibara, M.; Okada, K. Tetrahedron 1984, 40, 1767-1781. (f) Takahashi, T.; Ootake, A.; Yamada, H.; Tsuji, J. Tetrahedron Lett. 1985, 26, 69-72. (g) Aburatani, M.; Takeuchi, T.; Mori, K. Agric. Biol. Chem. 1986, 50, 3043-3047. (h) Shen, Z.-W.; Zhou, W -S. J. Chem. Soc., Perkin Trans. 1 1990, 1765-1767. (i) Back, T. G.; Krishna, M. V. J. Org. Chem. 1991, 56, 454-457. (j) Zhou, W.-S.; Jiang, B.; Pan, X.-F. Tetrahedron 1992, 48, 1837-1852. (k) Back, T. G.; Blazecka, P. G., Krishna, M. V. Can. J. Chem. 1993, 71, 156-163. (l) Hazra, B. G.; Joshi, P. L.; Bahule, B. B.; Argade, N. P.; Pore, V. S.; Chordia, M. D. Tetrahedron 1994, 50, 2523-2532. See also ref 31.
21. For some leading examples, see: (a) Ishiguro, M.; Takatsuto, S.; Morisaki, M.; Ikekawa, N. J. Chem. Soc., Chem. Commun. 1980, 962-964. (b) Fung, S.; Siddall, J. B. J. Am. Chem. Soc. 1980, 102, 6580-6581. (c) Hayami, H.; Sato, M.; Kanemoto, S.; Morizawa, Y.; Oshima, K.; Nozaki, H. J. Am. Chem. Soc. 1983, 105, 4491-4492. (d) Sakakibara, M.; Mori, K. Agric. Biol. Chem. 1983, 47, 663-664. (e) Mori, K.; Sakakibara, M.; Okada, K. Tetrahedron 1984, 40, 1767-1781. (f) Takahashi, T.; Ootake, A.; Yamada, H.; Tsuji, J. Tetrahedron Lett. 1985, 26, 69-72. (g) Aburatani, M.; Takeuchi, T.; Mori, K. Agric. Biol. Chem. 1986, 50, 3043-3047. (h) Shen, Z.-W.; Zhou, W -S. J. Chem. Soc., Perkin Trans. 1 1990, 1765-1767. (i) Back, T. G.; Krishna, M. V. J. Org. Chem. 1991, 56, 454-457. (j) Zhou, W.-S.; Jiang, B.; Pan, X.-F. Tetrahedron 1992, 48, 1837-1852. (k) Back, T. G.; Blazecka, P. G., Krishna, M. V. Can. J. Chem. 1993, 71, 156-163. (l) Hazra, B. G.; Joshi, P. L.; Bahule, B. B.; Argade, N. P.; Pore, V. S.; Chordia, M. D. Tetrahedron 1994, 50, 2523-2532. See also ref 31.
22. For some leading examples, see: (a) Ishiguro, M.; Takatsuto, S.; Morisaki, M.; Ikekawa, N. J. Chem. Soc., Chem. Commun. 1980, 962-964. (b) Fung, S.; Siddall, J. B. J. Am. Chem. Soc. 1980, 102, 6580-6581. (c) Hayami, H.; Sato, M.; Kanemoto, S.; Morizawa, Y.; Oshima, K.; Nozaki, H. J. Am. Chem. Soc. 1983, 105, 4491-4492. (d) Sakakibara, M.; Mori, K. Agric. Biol. Chem. 1983, 47, 663-664. (e) Mori, K.; Sakakibara, M.; Okada, K. Tetrahedron 1984, 40, 1767-1781. (f) Takahashi, T.; Ootake, A.; Yamada, H.; Tsuji, J. Tetrahedron Lett. 1985, 26, 69-72. (g) Aburatani, M.; Takeuchi, T.; Mori, K. Agric. Biol. Chem. 1986, 50, 3043-3047. (h) Shen, Z.-W.; Zhou, W -S. J. Chem. Soc., Perkin Trans. 1 1990, 1765-1767. (i) Back, T. G.; Krishna, M. V. J. Org. Chem. 1991, 56, 454-457. (j) Zhou, W.-S.; Jiang, B.; Pan, X.-F. Tetrahedron 1992, 48, 1837-1852. (k) Back, T. G.; Blazecka, P. G., Krishna, M. V. Can. J. Chem. 1993, 71, 156-163. (l) Hazra, B. G.; Joshi, P. L.; Bahule, B. B.; Argade, N. P.; Pore, V. S.; Chordia, M. D. Tetrahedron 1994, 50, 2523-2532. See also ref 31.
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30. (a) Anastasia, M.; Allevi, P.; Ciuffreda, P.; Fiecchi, A.; Scala, A. J. Org. Chem. 1984, 49, 4297-4300.
31. (b) Zhou, W.-S.; Tian, W.-S. Tetrahedron 1987, 43, 3705-3712.
32. (c) Zhou, W.-S.; Jiang, B.; Pan, X. J. Chem. Soc., Chem. Commun. 1989, 612-614.
33. (d) Honda, T.; Keino, K.; Tsubuki, M. J. Chem. Soc., Chem. Commun. 1990, 650-652.
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35. (a) Mori, K.; Sakakibara, M.; Ichikawa, Y.; Ueda, H.; Okada, K.; Umemura, T.; Yabuta, G.; Kuwahara, S.; Kondo, M. Tetrahedron 1982, 38, 2099-2109.
36. (b) Anastasia, M.; Ciuffreda, P.; Fiecci, A. J. Chem. Soc., Perkin Trans 1 1983, 379-382.
37. (c) Takatsuto, S.; Ikekawa, N. Chem. Pharm. Bull. 1985, 32, 2001-2004.
38. Marino, J. P.; Viso, A.; Fernández de la Pradilla, R.; Fernández, P. J. Org. Chem. 1991, 56, 1349-1351.
39. For the proposed predominate conformations in solution of A and B diastereomeric mesylates showing the most favored approach of the cuprate, see ref 9.
40. (a) Huang, L.-F.; Zhou, W.-S.; Sun, L.-Q.; Pan, X.-F. J. Chem. Soc., Perkin Trans. 1 1993, 1683-1686.
41. (b) McMorris, T. C.; Patil, P. A. J. Org. Chem. 1993, 58, 2338-2339.
42. (c) Brosa, C.; Peracaula, R.; Puig, R.; Ventura, M. Tetrahedron Lett. 1992, 33, 7057-7060.
43. (d) Zhou, W.-S.; Huang, L.-F.; Sun, L.-Q.; Pan, X.-F. Tetrahedron Lett. 1991, 32, 6745-6748.
44. (a) Lohray, B. B. Tetrahedron: Asymmetry 1992, 3, 1317-1349.
45. (b) Sharpless, K. B.; Amberg, W.; Bennani, Y. L.; Crispino, G. A.; Hartung, J.; Jeong, K.-S.; Kwong, H.-L ; Morikawa, K.; Wang, Z.-M.; Xu, D.; Zhang, X.-L. J. Org. Chem. 1992, 57, 2768-2771.
46. Easily available from stigmasterol; see: (a) Anderson, G. D.; Thomas, J. P.; Djerassi, C.; Fayos, J.; Clardy, J. J. Am. Chem. Soc. 1975, 97, 388-394. (b) Salmond, W. G.; Sobala, M. C. Tetrahedron Lett. 1977, 20, 1695-1698.
47. Easily available from stigmasterol; see: (a) Anderson, G. D.; Thomas, J. P.; Djerassi, C.; Fayos, J.; Clardy, J. J. Am. Chem. Soc. 1975, 97, 388-394. (b) Salmond, W. G.; Sobala, M. C. Tetrahedron Lett. 1977, 20, 1695-1698.
48. For analogous structural assignments in similar products, see refs 5b, c, e, and k and ref 31.
49. (a) Posner, G. H.; Mallamo, J. P.; Miura, K.; Hulce, M. Pure Appl. Chem. 1981, 53, 2307-2314 and references cited therein.
50. (b) Cheng, H.-C.; Yan, T.-H. Tetrahedron Lett. 1990, 31, 673-676.
51. (c) Solladie, G.; Moine, G. J. Am. Chem. Soc. 1984, 106, 6097-6098.
52. (d) Fawcett, J.; House, S.; Jenkins, P. R.; Lawrence, N. J.; Russell, D. R. J. Chem. Soc., Perkin Trans 1 1993, 67-72.
53. N2′ displacements on allylic mesylates, see: Ibuka, T.; Habashita, H.; Funakoshi, S.; Fujii, N.; Oguchi, Y.; Uyehara, T.; Yamamoto, Y. Angew. Chem., Int. Ed. Engl. 1990, 29, 801-803.
54. N2′ displacements on allylic mesylates, see: Ibuka, T.; Habashita, H.; Funakoshi, S.; Fujii, N.; Oguchi, Y.; Uyehara, T.; Yamamoto, Y. Angew. Chem., Int. Ed. Engl. 1990, 29, 801-803.
55. In all cases, any other conditions employing MsCl and/or different solvents and bases led to much slower transformations resulting in extensive decomposition of the reaction mixtures.
56. It should be pointed out that the use of Gilman cuprates resulted in formation of allenic products derived from 1,2-elimination of sulfoxide and mesyloxy groups. Recently we reported the preparation of allenes, of high enantiomeric purity, from unusually stabilized Cu(III) intermediates in this reaction; see: Fernández de la Pradilla, R.; Rubio, M. B.; Marino, J. P.; Viso, A. Tetrahedron Lett. 1992, 33, 4985-4988.
57. The stereochemistry of the double bond in all the adducts can be deduced from the chemical shift of the vinylic proton and by comparison with the model substrates, whose absolute configuration was unambiguously established by X-ray analyses (see ref 9).
58. (a) Park, G.; Okamura, W. H. Synth. Commun. 1991, 21, 1047-1054.
59. (b) Theobald, P. G.; Okamura, W. H. J. Org. Chem. 1990, 55, 741-750.
60. In the original procedure (ref 20), 4.0 equiv of organolithium reagent was used. For our substrates, we found much better yields and smooth, instantaneous transformations when only 1 25 equiv of t-BuLi is added in THF at -78°C.
61. Steele, J. A.; Mosettig, E. J. Am. Chem. Soc. 1963, 85, 571-572.
62. Takatsuto, S.; Ikekawa, N. Chem. Pharm. Bull. 1982, 30, 4181-4185.
63. 2-PHAL were required for this transformation (see Experimental Section). The use of the commercially available AD-mix-βi reagent resulted in extremely slow olefin conversion.
64. In contrast with these results, Zhou (ref 10a) has reported identical selectivities (8:1) for ADH of stigmasterol and (24S)-ergosterol derivatives using monochinchona ligands, DHQD-PHN and DHQD-p-chlorobenzoate, respectively. The spectral and physical data of (+)-12β, identical to those reported in the literature, confirms the stereochemistry of all the intermediates (see Experimental Section).
65. All attempts to interconvert the allylic alcohols 8a and b failed. A large number of conditions for the Mitsunobu protocol or the inversion of the mesylate derivative of (+)-8b were unsuccessful. For similar puzzling observations where inversion of propargylic C-22 steroidal alcohols afforded very low yields, see ref 5e.
66. For an elegant approach to brassinosteroids taking advantage of this concept, see: Furuta, T., Yamamoto, Y. J. Org. Chem. 1992, 57, 2981-2982.
67. See: Lodge, E. P.; Heathcock, C. H. J. Am. Chem. Soc. 1987, 109, 3353-3361 and references cited therein.
68. At this point, a more important influence of the steroid framework cannot be ruled out. More detailed studies to determine if the chirality at sulfur can control the Cram selectivity in additions to different α-branched chiral aldehydes are underway.
69. 2O at -35°C followed by addition of iodine (2.0 equiv) 84%; see: (a) Alexakis, A.; Cahiez, G.; Normant, J. F ; Villieras, J. Bull. Soc. Chim. Fr. 1977, 693-698. (b) Vermeer, P.; de Graaf, C.; Meijer, J. Recl. Trav. Chim. Pays-Bas 1974, 93, 24-25.
70. 2O at -35°C followed by addition of iodine (2.0 equiv) 84%; see: (a) Alexakis, A.; Cahiez, G.; Normant, J. F ; Villieras, J. Bull. Soc. Chim. Fr. 1977, 693-698. (b) Vermeer, P.; de Graaf, C.; Meijer, J. Recl. Trav. Chim. Pays-Bas 1974, 93, 24-25.
71. 2O at -35°C followed by addition of iodine (2.0 equiv) 84%; see: (a) Alexakis, A.; Cahiez, G.; Normant, J. F ; Villieras, J. Bull. Soc. Chim. Fr. 1977, 693-698. (b) Vermeer, P.; de Graaf, C.; Meijer, J. Recl. Trav. Chim. Pays-Bas 1974, 93, 24-25.
72. For similar results using an analogous 1-iodovinyl silane, see: Khripach, V. A.; Zhabinskiy, V. N.; Olkhovick, V. K. Tetrahedron Lett. 1990, 31, 4937-4940.
73. (a) Pitchen, P.; Dunach, E.; Deshmunkh, M. N.; Kagan, H. B. J. Am. Chem. Soc. 1984, 106, 8188-8193.
74. (b) Di Furia, F.; Modena, G.; Seraglia, R. Synthesis 1984, 325-326.
75. The directing effect of a hydroxyl group in m-CPBA diastereoselective oxidation of 10-sulfinyl isoborneols is known; see: Arai, Y.; Matsui, M.; Koizurai, T. Synthesis 1990, 320-323.
76. Davis, F. A.; Thimma Reddy, R.; Han, W.; Carroll, P. J. J. Am. Chem. Soc. 1992, 114, 1428-1437. For an account, see: Davis, F. A.; Thimma Reddy, R.; Han, W.; Reddy, R. E Pure Appl. Chem. 1993, 65, 633-640.
77. Davis, F. A.; Thimma Reddy, R.; Han, W.; Carroll, P. J. J. Am. Chem. Soc. 1992, 114, 1428-1437. For an account, see: Davis, F. A.; Thimma Reddy, R.; Han, W.; Reddy, R. E Pure Appl. Chem. 1993, 65, 633-640.
78. Marino, J. P.; Fernández de la Pradilla, R.; et al. Manuscript in preparation.
79. Watson, S. C.; Eastham, J. J. Organomet. Chem. 1967, 9, 165-168.
80. Prepared by the Homer-Wittig procedure; see: Mikolajczyk, M.; Midura, W.; Grzejszczak, S.; Zatorski, A.; Chefczynska, A. J. Org. Chem. 1978, 43, 473-478.
81. Prepared from commercially available 1-bromo-1-propene.