Total syntheses of (+)-australine and (-)-7-epialexine

Journal of Organic Chemistry

Volumn 65, Issue 18, 2000, Pages 5785-5793

  Pearson, William H ^a   Hines, Jennifer V ^a,b  

^a UNIVERSITY OF MICHIGAN   (United States)

^b OHIO UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

7 EPIALEXINE; ALKALOID DERIVATIVE; AUSTRALINE; PYRROLIZIDINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL MODIFICATION; CHEMICAL REACTION; CYCLIZATION; DRUG STRUCTURE; DRUG SYNTHESIS; EPOXIDATION; STEREOCHEMISTRY; STRUCTURE ANALYSIS;

AZIDES; OXIDATION-REDUCTION; PYRROLIZIDINE ALKALOIDS; SPECTRUM ANALYSIS; STEREOISOMERISM;

EID: 0033833094     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo000689q     Document Type: Article

References (55)

1. (a) Fellows, L. E.; Fleet, G. W. In Natural Products Isolation; Wagman, G. H., Copper, R., Eds.; Elsevier: Amsterdam, 1988; p 540.
2. (b) Nash, R. J.; Watson, A. A.; Asano, N. In Alkaloids: Chemical and Biological Perspectives; Pelletier, S. W, Ed.; Elsevier: Oxford, 1996; Vol. 11; pp 345-376.
3. (c) Liddell, J. R. Nat. Prod. Rep. 1986, 187-193.
4. Isolation of alexine: Nash, R. J.; Fellows, L. E.; Dring, J. V.; Fleet, G. W. J.; Derome, A. E.; Hamor, T. A.; Scofield, A. M.; Watkin, D. J. Tetrahedron Lett. 1988, 29, 2487-2490.
5. Synthesis of alexine: Fleet, G. W. J.; Haraldsson, M.; Nash, R. J.; Fellows, L. E. Tetrahedron Lett. 1988, 29, 5441-5444. The syntheses of 3-epi- and 7-epialexine are also reported.
6. Isolation of australine: Molyneux, R. J.; Benson, M.; Wong, R. Y.; Tropea, J. E.; Elbein, A. D. J. Nat. Prod. 1988, 51, 1198-1206.
7. Syntheses of australine: (a) Pearson, W. H.; Hines, J. V. Tetrahedron Lett. 1991, 32, 5513-5516 (the synthesis of 7-epiaustraline reported in this paper was actually a synthesis of australine; see text for explanation). (b) White, J. D.; Hrnciar, P.; Yokochi, A. F. T. J. Am. Chem. Soc. 1998, 120, 7359-7360. (c) Denmark, S. E.; Martinborough, E. A. J. Am. Chem. Soc. 1999, 121, 3046-3056. For a synthesis of australine from castanospermine, see: (d) Furneaux, R. H.; Gainsford, G. J.; Mason, J. M.; Tyler, P. C. Tetrahedron 1994, 50, 2131-2160.
8. Syntheses of australine: (a) Pearson, W. H.; Hines, J. V. Tetrahedron Lett. 1991, 32, 5513-5516 (the synthesis of 7-epiaustraline reported in this paper was actually a synthesis of australine; see text for explanation). (b) White, J. D.; Hrnciar, P.; Yokochi, A. F. T. J. Am. Chem. Soc. 1998, 120, 7359-7360. (c) Denmark, S. E.; Martinborough, E. A. J. Am. Chem. Soc. 1999, 121, 3046-3056. For a synthesis of australine from castanospermine, see: (d) Furneaux, R. H.; Gainsford, G. J.; Mason, J. M.; Tyler, P. C. Tetrahedron 1994, 50, 2131-2160.
9. Syntheses of australine: (a) Pearson, W. H.; Hines, J. V. Tetrahedron Lett. 1991, 32, 5513-5516 (the synthesis of 7-epiaustraline reported in this paper was actually a synthesis of australine; see text for explanation). (b) White, J. D.; Hrnciar, P.; Yokochi, A. F. T. J. Am. Chem. Soc. 1998, 120, 7359-7360. (c) Denmark, S. E.; Martinborough, E. A. J. Am. Chem. Soc. 1999, 121, 3046-3056. For a synthesis of australine from castanospermine, see: (d) Furneaux, R. H.; Gainsford, G. J.; Mason, J. M.; Tyler, P. C. Tetrahedron 1994, 50, 2131-2160.
10. Syntheses of australine: (a) Pearson, W. H.; Hines, J. V. Tetrahedron Lett. 1991, 32, 5513-5516 (the synthesis of 7-epiaustraline reported in this paper was actually a synthesis of australine; see text for explanation). (b) White, J. D.; Hrnciar, P.; Yokochi, A. F. T. J. Am. Chem. Soc. 1998, 120, 7359-7360. (c) Denmark, S. E.; Martinborough, E. A. J. Am. Chem. Soc. 1999, 121, 3046-3056. For a synthesis of australine from castanospermine, see: (d) Furneaux, R. H.; Gainsford, G. J.; Mason, J. M.; Tyler, P. C. Tetrahedron 1994, 50, 2131-2160.
11. For the synthesis of ring-expanded analogues of australine and alexine, see: Pearson, W. H.; Hembre, E. J. J. Org. Chem. 1996, 61, 5545-5556.
12. For a report of the isolation of 7-epiaustraline, later found to be australine, see: (a) Nash, R. J.; Fellows, L. E.; Dring, J. V.; Fleet, G. W. J.; Girdhar, A.; Ramsden, N. G.; Peach, J. M.; Hegarty, M. P.; Scofield, A. M. Phytochemistry 1990, 29, 111-114. For a report of the synthesis of 7-epiaustraline, later found to be australine, see ref 6a. For an unambiguous synthesis of 7-epiaustraline, see: (b) Denmark, S. E.; Herbert, B. J. Am. Chem. Soc. 1998, 120, 7357-7358. (c) Denmark, S. E.; Herbert, B. J. Org. Chem. 2000, 65, 2887-2896. See the text for a full explanation.
13. For a report of the isolation of 7-epiaustraline, later found to be australine, see: (a) Nash, R. J.; Fellows, L. E.; Dring, J. V.; Fleet, G. W. J.; Girdhar, A.; Ramsden, N. G.; Peach, J. M.; Hegarty, M. P.; Scofield, A. M. Phytochemistry 1990, 29, 111-114. For a report of the synthesis of 7-epiaustraline, later found to be australine, see ref 6a. For an unambiguous synthesis of 7-epiaustraline, see: (b) Denmark, S. E.; Herbert, B. J. Am. Chem. Soc. 1998, 120, 7357-7358. (c) Denmark, S. E.; Herbert, B. J. Org. Chem. 2000, 65, 2887-2896. See the text for a full explanation.
14. For a report of the isolation of 7-epiaustraline, later found to be australine, see: (a) Nash, R. J.; Fellows, L. E.; Dring, J. V.; Fleet, G. W. J.; Girdhar, A.; Ramsden, N. G.; Peach, J. M.; Hegarty, M. P.; Scofield, A. M. Phytochemistry 1990, 29, 111-114. For a report of the synthesis of 7-epiaustraline, later found to be australine, see ref 6a. For an unambiguous synthesis of 7-epiaustraline, see: (b) Denmark, S. E.; Herbert, B. J. Am. Chem. Soc. 1998, 120, 7357-7358. (c) Denmark, S. E.; Herbert, B. J. Org. Chem. 2000, 65, 2887-2896. See the text for a full explanation.
15. For an excellent review of the chemistry and biochemistry of alkaloidal glycosidase inhibitors, see: Iminosugars as Glycosidase Inhibitors; Stütz, A. E., Ed.; Wiley-VCH: Weinheim, 1999.
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20. For a preliminary report of this work, see ref 6a.
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23. For related one-pot double cyclizations using azido epoxides or amino epoxides, see refs 6a, 7, and: (a) Setoi, H.; Takeno, H.; Hashimoto, M. J. Org. Chem. 1985, 50, 3948-3950. (b) Setoi, H.; Takeno, H.; Hashimoto, M. Tetrahedron Lett. 1985, 26, 4617-4620. (c) Kim, Y. G.; Cha, J. K. Tetrahedron Lett. 1989, 30, 5721-5724. (d) Pearson, W. H.; Bergmeier, S. C.; Williams, J. P. J. Org. Chem. 1992, 57, 3977-3987. (e) Ina, H.; Kibayashi, C. J. Org. Chem. 1993, 58, 52- 61. (f) Jirousek, M. R.; Cheung, A. W.-H.; Babine, R. E.; Sass, P. M.; Schow, S. R.; Wick, M. M. Tetrahedron Lett. 1993, 34, 3671-3674. (g) Kim, N.-S.; Choi, J.-R.; Cha, J. K. J. Org. Chem 1993, 58, 7096-7099. (h) Poitout, L.; Le Merrer, Y.; Depezay, J.-C. Tetrahedron Lett. 1994, 35, 3293-3296. (i) Lohray, B. B.; Jayamma, Y. and Chatterjee, M. J. Org. Chem. 1995, 60, 5958-5960. (j) Pearson, W. H.; Hembre, E. J. J. Org. Chem. 1996, 61, 5537-5545. (k) Hembre, E. J.; Pearson, W. H. Tetrahedron 1997, 53, 11021-11032.
24. For related one-pot double cyclizations using azido epoxides or amino epoxides, see refs 6a, 7, and: (a) Setoi, H.; Takeno, H.; Hashimoto, M. J. Org. Chem. 1985, 50, 3948-3950. (b) Setoi, H.; Takeno, H.; Hashimoto, M. Tetrahedron Lett. 1985, 26, 4617-4620. (c) Kim, Y. G.; Cha, J. K. Tetrahedron Lett. 1989, 30, 5721-5724. (d) Pearson, W. H.; Bergmeier, S. C.; Williams, J. P. J. Org. Chem. 1992, 57, 3977-3987. (e) Ina, H.; Kibayashi, C. J. Org. Chem. 1993, 58, 52- 61. (f) Jirousek, M. R.; Cheung, A. W.-H.; Babine, R. E.; Sass, P. M.; Schow, S. R.; Wick, M. M. Tetrahedron Lett. 1993, 34, 3671-3674. (g) Kim, N.-S.; Choi, J.-R.; Cha, J. K. J. Org. Chem 1993, 58, 7096-7099. (h) Poitout, L.; Le Merrer, Y.; Depezay, J.-C. Tetrahedron Lett. 1994, 35, 3293-3296. (i) Lohray, B. B.; Jayamma, Y. and Chatterjee, M. J. Org. Chem. 1995, 60, 5958-5960. (j) Pearson, W. H.; Hembre, E. J. J. Org. Chem. 1996, 61, 5537-5545. (k) Hembre, E. J.; Pearson, W. H. Tetrahedron 1997, 53, 11021-11032.
25. For related one-pot double cyclizations using azido epoxides or amino epoxides, see refs 6a, 7, and: (a) Setoi, H.; Takeno, H.; Hashimoto, M. J. Org. Chem. 1985, 50, 3948-3950. (b) Setoi, H.; Takeno, H.; Hashimoto, M. Tetrahedron Lett. 1985, 26, 4617-4620. (c) Kim, Y. G.; Cha, J. K. Tetrahedron Lett. 1989, 30, 5721-5724. (d) Pearson, W. H.; Bergmeier, S. C.; Williams, J. P. J. Org. Chem. 1992, 57, 3977-3987. (e) Ina, H.; Kibayashi, C. J. Org. Chem. 1993, 58, 52- 61. (f) Jirousek, M. R.; Cheung, A. W.-H.; Babine, R. E.; Sass, P. M.; Schow, S. R.; Wick, M. M. Tetrahedron Lett. 1993, 34, 3671-3674. (g) Kim, N.-S.; Choi, J.-R.; Cha, J. K. J. Org. Chem 1993, 58, 7096-7099. (h) Poitout, L.; Le Merrer, Y.; Depezay, J.-C. Tetrahedron Lett. 1994, 35, 3293-3296. (i) Lohray, B. B.; Jayamma, Y. and Chatterjee, M. J. Org. Chem. 1995, 60, 5958-5960. (j) Pearson, W. H.; Hembre, E. J. J. Org. Chem. 1996, 61, 5537-5545. (k) Hembre, E. J.; Pearson, W. H. Tetrahedron 1997, 53, 11021-11032.
26. For related one-pot double cyclizations using azido epoxides or amino epoxides, see refs 6a, 7, and: (a) Setoi, H.; Takeno, H.; Hashimoto, M. J. Org. Chem. 1985, 50, 3948-3950. (b) Setoi, H.; Takeno, H.; Hashimoto, M. Tetrahedron Lett. 1985, 26, 4617-4620. (c) Kim, Y. G.; Cha, J. K. Tetrahedron Lett. 1989, 30, 5721-5724. (d) Pearson, W. H.; Bergmeier, S. C.; Williams, J. P. J. Org. Chem. 1992, 57, 3977-3987. (e) Ina, H.; Kibayashi, C. J. Org. Chem. 1993, 58, 52- 61. (f) Jirousek, M. R.; Cheung, A. W.-H.; Babine, R. E.; Sass, P. M.; Schow, S. R.; Wick, M. M. Tetrahedron Lett. 1993, 34, 3671-3674. (g) Kim, N.-S.; Choi, J.-R.; Cha, J. K. J. Org. Chem 1993, 58, 7096-7099. (h) Poitout, L.; Le Merrer, Y.; Depezay, J.-C. Tetrahedron Lett. 1994, 35, 3293-3296. (i) Lohray, B. B.; Jayamma, Y. and Chatterjee, M. J. Org. Chem. 1995, 60, 5958-5960. (j) Pearson, W. H.; Hembre, E. J. J. Org. Chem. 1996, 61, 5537-5545. (k) Hembre, E. J.; Pearson, W. H. Tetrahedron 1997, 53, 11021-11032.
27. For related one-pot double cyclizations using azido epoxides or amino epoxides, see refs 6a, 7, and: (a) Setoi, H.; Takeno, H.; Hashimoto, M. J. Org. Chem. 1985, 50, 3948-3950. (b) Setoi, H.; Takeno, H.; Hashimoto, M. Tetrahedron Lett. 1985, 26, 4617-4620. (c) Kim, Y. G.; Cha, J. K. Tetrahedron Lett. 1989, 30, 5721-5724. (d) Pearson, W. H.; Bergmeier, S. C.; Williams, J. P. J. Org. Chem. 1992, 57, 3977-3987. (e) Ina, H.; Kibayashi, C. J. Org. Chem. 1993, 58, 52-61. (f) Jirousek, M. R.; Cheung, A. W.-H.; Babine, R. E.; Sass, P. M.; Schow, S. R.; Wick, M. M. Tetrahedron Lett. 1993, 34, 3671-3674. (g) Kim, N.-S.; Choi, J.-R.; Cha, J. K. J. Org. Chem 1993, 58, 7096-7099. (h) Poitout, L.; Le Merrer, Y.; Depezay, J.-C. Tetrahedron Lett. 1994, 35, 3293-3296. (i) Lohray, B. B.; Jayamma, Y. and Chatterjee, M. J. Org. Chem. 1995, 60, 5958-5960. (j) Pearson, W. H.; Hembre, E. J. J. Org. Chem. 1996, 61, 5537-5545. (k) Hembre, E. J.; Pearson, W. H. Tetrahedron 1997, 53, 11021-11032.
28. For related one-pot double cyclizations using azido epoxides or amino epoxides, see refs 6a, 7, and: (a) Setoi, H.; Takeno, H.; Hashimoto, M. J. Org. Chem. 1985, 50, 3948-3950. (b) Setoi, H.; Takeno, H.; Hashimoto, M. Tetrahedron Lett. 1985, 26, 4617-4620. (c) Kim, Y. G.; Cha, J. K. Tetrahedron Lett. 1989, 30, 5721-5724. (d) Pearson, W. H.; Bergmeier, S. C.; Williams, J. P. J. Org. Chem. 1992, 57, 3977-3987. (e) Ina, H.; Kibayashi, C. J. Org. Chem. 1993, 58, 52- 61. (f) Jirousek, M. R.; Cheung, A. W.-H.; Babine, R. E.; Sass, P. M.; Schow, S. R.; Wick, M. M. Tetrahedron Lett. 1993, 34, 3671-3674. (g) Kim, N.-S.; Choi, J.-R.; Cha, J. K. J. Org. Chem 1993, 58, 7096-7099. (h) Poitout, L.; Le Merrer, Y.; Depezay, J.-C. Tetrahedron Lett. 1994, 35, 3293-3296. (i) Lohray, B. B.; Jayamma, Y. and Chatterjee, M. J. Org. Chem. 1995, 60, 5958-5960. (j) Pearson, W. H.; Hembre, E. J. J. Org. Chem. 1996, 61, 5537-5545. (k) Hembre, E. J.; Pearson, W. H. Tetrahedron 1997, 53, 11021-11032.
29. For related one-pot double cyclizations using azido epoxides or amino epoxides, see refs 6a, 7, and: (a) Setoi, H.; Takeno, H.; Hashimoto, M. J. Org. Chem. 1985, 50, 3948-3950. (b) Setoi, H.; Takeno, H.; Hashimoto, M. Tetrahedron Lett. 1985, 26, 4617-4620. (c) Kim, Y. G.; Cha, J. K. Tetrahedron Lett. 1989, 30, 5721-5724. (d) Pearson, W. H.; Bergmeier, S. C.; Williams, J. P. J. Org. Chem. 1992, 57, 3977-3987. (e) Ina, H.; Kibayashi, C. J. Org. Chem. 1993, 58, 52- 61. (f) Jirousek, M. R.; Cheung, A. W.-H.; Babine, R. E.; Sass, P. M.; Schow, S. R.; Wick, M. M. Tetrahedron Lett. 1993, 34, 3671-3674. (g) Kim, N.-S.; Choi, J.-R.; Cha, J. K. J. Org. Chem 1993, 58, 7096-7099. (h) Poitout, L.; Le Merrer, Y.; Depezay, J.-C. Tetrahedron Lett. 1994, 35, 3293-3296. (i) Lohray, B. B.; Jayamma, Y. and Chatterjee, M. J. Org. Chem. 1995, 60, 5958-5960. (j) Pearson, W. H.; Hembre, E. J. J. Org. Chem. 1996, 61, 5537-5545. (k) Hembre, E. J.; Pearson, W. H. Tetrahedron 1997, 53, 11021-11032.
30. For related one-pot double cyclizations using azido epoxides or amino epoxides, see refs 6a, 7, and: (a) Setoi, H.; Takeno, H.; Hashimoto, M. J. Org. Chem. 1985, 50, 3948-3950. (b) Setoi, H.; Takeno, H.; Hashimoto, M. Tetrahedron Lett. 1985, 26, 4617-4620. (c) Kim, Y. G.; Cha, J. K. Tetrahedron Lett. 1989, 30, 5721-5724. (d) Pearson, W. H.; Bergmeier, S. C.; Williams, J. P. J. Org. Chem. 1992, 57, 3977-3987. (e) Ina, H.; Kibayashi, C. J. Org. Chem. 1993, 58, 52- 61. (f) Jirousek, M. R.; Cheung, A. W.-H.; Babine, R. E.; Sass, P. M.; Schow, S. R.; Wick, M. M. Tetrahedron Lett. 1993, 34, 3671-3674. (g) Kim, N.-S.; Choi, J.-R.; Cha, J. K. J. Org. Chem 1993, 58, 7096-7099. (h) Poitout, L.; Le Merrer, Y.; Depezay, J.-C. Tetrahedron Lett. 1994, 35, 3293-3296. (i) Lohray, B. B.; Jayamma, Y. and Chatterjee, M. J. Org. Chem. 1995, 60, 5958-5960. (j) Pearson, W. H.; Hembre, E. J. J. Org. Chem. 1996, 61, 5537-5545. (k) Hembre, E. J.; Pearson, W. H. Tetrahedron 1997, 53, 11021-11032.
31. For related one-pot double cyclizations using azido epoxides or amino epoxides, see refs 6a, 7, and: (a) Setoi, H.; Takeno, H.; Hashimoto, M. J. Org. Chem. 1985, 50, 3948-3950. (b) Setoi, H.; Takeno, H.; Hashimoto, M. Tetrahedron Lett. 1985, 26, 4617-4620. (c) Kim, Y. G.; Cha, J. K. Tetrahedron Lett. 1989, 30, 5721-5724. (d) Pearson, W. H.; Bergmeier, S. C.; Williams, J. P. J. Org. Chem. 1992, 57, 3977-3987. (e) Ina, H.; Kibayashi, C. J. Org. Chem. 1993, 58, 52- 61. (f) Jirousek, M. R.; Cheung, A. W.-H.; Babine, R. E.; Sass, P. M.; Schow, S. R.; Wick, M. M. Tetrahedron Lett. 1993, 34, 3671-3674. (g) Kim, N.-S.; Choi, J.-R.; Cha, J. K. J. Org. Chem 1993, 58, 7096-7099. (h) Poitout, L.; Le Merrer, Y.; Depezay, J.-C. Tetrahedron Lett. 1994, 35, 3293-3296. (i) Lohray, B. B.; Jayamma, Y. and Chatterjee, M. J. Org. Chem. 1995, 60, 5958-5960. (j) Pearson, W. H.; Hembre, E. J. J. Org. Chem. 1996, 61, 5537-5545. (k) Hembre, E. J.; Pearson, W. H. Tetrahedron 1997, 53, 11021-11032.
32. For related one-pot double cyclizations using azido epoxides or amino epoxides, see refs 6a, 7, and: (a) Setoi, H.; Takeno, H.; Hashimoto, M. J. Org. Chem. 1985, 50, 3948-3950. (b) Setoi, H.; Takeno, H.; Hashimoto, M. Tetrahedron Lett. 1985, 26, 4617-4620. (c) Kim, Y. G.; Cha, J. K. Tetrahedron Lett. 1989, 30, 5721-5724. (d) Pearson, W. H.; Bergmeier, S. C.; Williams, J. P. J. Org. Chem. 1992, 57, 3977-3987. (e) Ina, H.; Kibayashi, C. J. Org. Chem. 1993, 58, 52- 61. (f) Jirousek, M. R.; Cheung, A. W.-H.; Babine, R. E.; Sass, P. M.; Schow, S. R.; Wick, M. M. Tetrahedron Lett. 1993, 34, 3671-3674. (g) Kim, N.-S.; Choi, J.-R.; Cha, J. K. J. Org. Chem 1993, 58, 7096-7099. (h) Poitout, L.; Le Merrer, Y.; Depezay, J.-C. Tetrahedron Lett. 1994, 35, 3293-3296. (i) Lohray, B. B.; Jayamma, Y. and Chatterjee, M. J. Org. Chem. 1995, 60, 5958-5960. (j) Pearson, W. H.; Hembre, E. J. J. Org. Chem. 1996, 61, 5537-5545. (k) Hembre, E. J.; Pearson, W. H. Tetrahedron 1997, 53, 11021-11032.
33. For related one-pot double cyclizations using azido epoxides or amino epoxides, see refs 6a, 7, and: (a) Setoi, H.; Takeno, H.; Hashimoto, M. J. Org. Chem. 1985, 50, 3948-3950. (b) Setoi, H.; Takeno, H.; Hashimoto, M. Tetrahedron Lett. 1985, 26, 4617-4620. (c) Kim, Y. G.; Cha, J. K. Tetrahedron Lett. 1989, 30, 5721-5724. (d) Pearson, W. H.; Bergmeier, S. C.; Williams, J. P. J. Org. Chem. 1992, 57, 3977-3987. (e) Ina, H.; Kibayashi, C. J. Org. Chem. 1993, 58, 52- 61. (f) Jirousek, M. R.; Cheung, A. W.-H.; Babine, R. E.; Sass, P. M.; Schow, S. R.; Wick, M. M. Tetrahedron Lett. 1993, 34, 3671-3674. (g) Kim, N.-S.; Choi, J.-R.; Cha, J. K. J. Org. Chem 1993, 58, 7096-7099. (h) Poitout, L.; Le Merrer, Y.; Depezay, J.-C. Tetrahedron Lett. 1994, 35, 3293-3296. (i) Lohray, B. B.; Jayamma, Y. and Chatterjee, M. J. Org. Chem. 1995, 60, 5958-5960. (j) Pearson, W. H.; Hembre, E. J. J. Org. Chem. 1996, 61, 5537-5545. (k) Hembre, E. J.; Pearson, W. H. Tetrahedron 1997, 53, 11021-11032.
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