A New Synthetic Approach to Forskolin: Construction of the ABC Ring System from D-Galactose

Journal of Organic Chemistry

Volumn 62, Issue 20, 1997, Pages 6985-6990

  Hanna, Issam ^a   Wlodyka, Philippe ^a  

^a LABORATOIRE DE SYNTHÈSE ORGANIQUE   (France)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000298434     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970999h     Document Type: Article

References (49)

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2. For total syntheses of forskolin see: (a) Ziegler, F. E.; Jaynes, B. H.; Saindane, M. T. J. Am. Chem. Soc. 1987, 109, 8115-8116. (b) Hashimoto, S.; Sakata, S.; Sonegawa, M.; Ikegami, S. J. Am. Chem. Soc. 1988, 110, 3670-3672.
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7. For an exhaustive review on synthetic routes to forskolin see: Colombo, M. I.; Zinezuk, J.; Ruveda, E. A. Tetrahedron 1992, 48, 963-1037. For recent syntheses of the "Ziegler intermediate" see: Leclaire, M.; Pericaud, F.; Lallemand, J.-Y. J. Chem. Soc., Chem. Commun. 1995, 1333-1334. Anies, C.; Pancrazi, A.; Lallemand, J.-Y.; Prangé, T. Bull. Soc. Chim. Fr, 1997, 134, 203-222.
8. For an exhaustive review on synthetic routes to forskolin see: Colombo, M. I.; Zinezuk, J.; Ruveda, E. A. Tetrahedron 1992, 48, 963-1037. For recent syntheses of the "Ziegler intermediate" see: Leclaire, M.; Pericaud, F.; Lallemand, J.-Y. J. Chem. Soc., Chem. Commun. 1995, 1333-1334. Anies, C.; Pancrazi, A.; Lallemand, J.-Y.; Prangé, T. Bull. Soc. Chim. Fr, 1997, 134, 203-222.
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13. For recent examples see: (a) Lopez, J. C.; Lameignière, E.; Burnouf, C.; Laborde, A. A.; Ghini, A. A.; Olesker, A.; Lukacs, G. Tetrahedron 1993, 49, 7701-7722. (b) Lopez, J. C.; Gomez, A. M.; Fraser-Reid, B. J. Chem. Soc., Chem. Commun. 1993, 762-764. (c) Herscovici, J.; Delatre, S.; Boumaïza, L.; Antonakis, K. J. Org. Chem. 1993, 58, 3928-3937. (d) Giuliano, R. M.; Jordan, A. D., Jr.; Gauthier, A. D.; Hoogsteen, K. J. Org. Chem. 1993, 58, 4979-4988. (e) Tsang, R. B.; Fraser-Reid, B. J. Org. Chem. 1992, 57, 1065-1067. (f) Bonnert, B. V.; Davies, M. J.; Howarth, J.; Jenkins, P. R.; Lawrence, N. J. J. Chem. Soc., Perkin Trans. 1 1992, 27-29. (g) Hanessian, S.; Faucher, A.-M. J. Org. Chem. 1991, 65, 2947-2949.
14. For recent examples see: (a) Lopez, J. C.; Lameignière, E.; Burnouf, C.; Laborde, A. A.; Ghini, A. A.; Olesker, A.; Lukacs, G. Tetrahedron 1993, 49, 7701-7722. (b) Lopez, J. C.; Gomez, A. M.; Fraser-Reid, B. J. Chem. Soc., Chem. Commun. 1993, 762-764. (c) Herscovici, J.; Delatre, S.; Boumaïza, L.; Antonakis, K. J. Org. Chem. 1993, 58, 3928-3937. (d) Giuliano, R. M.; Jordan, A. D., Jr.; Gauthier, A. D.; Hoogsteen, K. J. Org. Chem. 1993, 58, 4979-4988. (e) Tsang, R. B.; Fraser-Reid, B. J. Org. Chem. 1992, 57, 1065-1067. (f) Bonnert, B. V.; Davies, M. J.; Howarth, J.; Jenkins, P. R.; Lawrence, N. J. J. Chem. Soc., Perkin Trans. 1 1992, 27-29. (g) Hanessian, S.; Faucher, A.-M. J. Org. Chem. 1991, 65, 2947-2949.
15. For recent examples see: (a) Lopez, J. C.; Lameignière, E.; Burnouf, C.; Laborde, A. A.; Ghini, A. A.; Olesker, A.; Lukacs, G. Tetrahedron 1993, 49, 7701-7722. (b) Lopez, J. C.; Gomez, A. M.; Fraser-Reid, B. J. Chem. Soc., Chem. Commun. 1993, 762-764. (c) Herscovici, J.; Delatre, S.; Boumaïza, L.; Antonakis, K. J. Org. Chem. 1993, 58, 3928-3937. (d) Giuliano, R. M.; Jordan, A. D., Jr.; Gauthier, A. D.; Hoogsteen, K. J. Org. Chem. 1993, 58, 4979-4988. (e) Tsang, R. B.; Fraser-Reid, B. J. Org. Chem. 1992, 57, 1065-1067. (f) Bonnert, B. V.; Davies, M. J.; Howarth, J.; Jenkins, P. R.; Lawrence, N. J. J. Chem. Soc., Perkin Trans. 1 1992, 27-29. (g) Hanessian, S.; Faucher, A.-M. J. Org. Chem. 1991, 65, 2947-2949.
16. For recent examples see: (a) Lopez, J. C.; Lameignière, E.; Burnouf, C.; Laborde, A. A.; Ghini, A. A.; Olesker, A.; Lukacs, G. Tetrahedron 1993, 49, 7701-7722. (b) Lopez, J. C.; Gomez, A. M.; Fraser-Reid, B. J. Chem. Soc., Chem. Commun. 1993, 762-764. (c) Herscovici, J.; Delatre, S.; Boumaïza, L.; Antonakis, K. J. Org. Chem. 1993, 58, 3928-3937. (d) Giuliano, R. M.; Jordan, A. D., Jr.; Gauthier, A. D.; Hoogsteen, K. J. Org. Chem. 1993, 58, 4979-4988. (e) Tsang, R. B.; Fraser-Reid, B. J. Org. Chem. 1992, 57, 1065-1067. (f) Bonnert, B. V.; Davies, M. J.; Howarth, J.; Jenkins, P. R.; Lawrence, N. J. J. Chem. Soc., Perkin Trans. 1 1992, 27-29. (g) Hanessian, S.; Faucher, A.-M. J. Org. Chem. 1991, 65, 2947-2949.
17. For recent examples see: (a) Lopez, J. C.; Lameignière, E.; Burnouf, C.; Laborde, A. A.; Ghini, A. A.; Olesker, A.; Lukacs, G. Tetrahedron 1993, 49, 7701-7722. (b) Lopez, J. C.; Gomez, A. M.; Fraser-Reid, B. J. Chem. Soc., Chem. Commun. 1993, 762-764. (c) Herscovici, J.; Delatre, S.; Boumaïza, L.; Antonakis, K. J. Org. Chem. 1993, 58, 3928-3937. (d) Giuliano, R. M.; Jordan, A. D., Jr.; Gauthier, A. D.; Hoogsteen, K. J. Org. Chem. 1993, 58, 4979-4988. (e) Tsang, R. B.; Fraser-Reid, B. J. Org. Chem. 1992, 57, 1065-1067. (f) Bonnert, B. V.; Davies, M. J.; Howarth, J.; Jenkins, P. R.; Lawrence, N. J. J. Chem. Soc., Perkin Trans. 1 1992, 27-29. (g) Hanessian, S.; Faucher, A.-M. J. Org. Chem. 1991, 65, 2947-2949.
18. For recent examples see: (a) Lopez, J. C.; Lameignière, E.; Burnouf, C.; Laborde, A. A.; Ghini, A. A.; Olesker, A.; Lukacs, G. Tetrahedron 1993, 49, 7701-7722. (b) Lopez, J. C.; Gomez, A. M.; Fraser-Reid, B. J. Chem. Soc., Chem. Commun. 1993, 762-764. (c) Herscovici, J.; Delatre, S.; Boumaïza, L.; Antonakis, K. J. Org. Chem. 1993, 58, 3928-3937. (d) Giuliano, R. M.; Jordan, A. D., Jr.; Gauthier, A. D.; Hoogsteen, K. J. Org. Chem. 1993, 58, 4979-4988. (e) Tsang, R. B.; Fraser-Reid, B. J. Org. Chem. 1992, 57, 1065-1067. (f) Bonnert, B. V.; Davies, M. J.; Howarth, J.; Jenkins, P. R.; Lawrence, N. J. J. Chem. Soc., Perkin Trans. 1 1992, 27-29. (g) Hanessian, S.; Faucher, A.-M. J. Org. Chem. 1991, 65, 2947-2949.
19. For recent examples see: (a) Lopez, J. C.; Lameignière, E.; Burnouf, C.; Laborde, A. A.; Ghini, A. A.; Olesker, A.; Lukacs, G. Tetrahedron 1993, 49, 7701-7722. (b) Lopez, J. C.; Gomez, A. M.; Fraser-Reid, B. J. Chem. Soc., Chem. Commun. 1993, 762-764. (c) Herscovici, J.; Delatre, S.; Boumaïza, L.; Antonakis, K. J. Org. Chem. 1993, 58, 3928-3937. (d) Giuliano, R. M.; Jordan, A. D., Jr.; Gauthier, A. D.; Hoogsteen, K. J. Org. Chem. 1993, 58, 4979-4988. (e) Tsang, R. B.; Fraser-Reid, B. J. Org. Chem. 1992, 57, 1065-1067. (f) Bonnert, B. V.; Davies, M. J.; Howarth, J.; Jenkins, P. R.; Lawrence, N. J. J. Chem. Soc., Perkin Trans. 1 1992, 27-29. (g) Hanessian, S.; Faucher, A.-M. J. Org. Chem. 1991, 65, 2947-2949.
20. Portions of this work have been reported in preliminary form: Hanna, I.; Lallemand, J.-Y.; Wlodyka, P. Tetrahedron Lett. 1994, 35, 6685-6688.
21. (a) Danishefsky, S. J.; Kerwin, J. F., Jr. J. Org. Chem. 1982, 47, 3803-3805.
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23. Although this starting material is commercially available, its price is rather exorbitant. We therefore prepared it according to the published procedure: Kozikowski, A. P.; Jaemoon, L. J. Org. Chem. 1990, 55, 863-870.
24. Ireland, R. E.; Smith, M. G. J. Am. Chem. Soc. 1988, 110, 854-860 and references cited therein.
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26. It is worthy of note that first attempts to effect this rearrangement in refluxing benzene gave mostly the starting ester. For a study on the stereoelectronic effect on the Claisen rearrangement of carbohydrate glycal ketene acetals see: Curran, D. P.; Suh, Y.-G. Carbohyr. Res. 1987, 117, 161-191.
27. The next steps were performed on this mixture, the asymmetry at this center being destroyed later in the synthesis.
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38. For recent examples of related IMDA cyclization see: Zoller, T.; Uguen, D.; DeCian, A.; Fischer, J.; Sablé, S. Tetrahedron Lett. 1997, 38, 3409-3412. Shishido, K.; Omodani, T.; Shibuya, M. J. Chem. Soc., Perkin Trans. 1 1991, 2285-2287. Shing, T. K. M.; Tang, Y. Tetrahedron 1990, 46, 2187-2194.
39. For recent examples of related IMDA cyclization see: Zoller, T.; Uguen, D.; DeCian, A.; Fischer, J.; Sablé, S. Tetrahedron Lett. 1997, 38, 3409-3412. Shishido, K.; Omodani, T.; Shibuya, M. J. Chem. Soc., Perkin Trans. 1 1991, 2285-2287. Shing, T. K. M.; Tang, Y. Tetrahedron 1990, 46, 2187-2194.
40. For recent examples of related IMDA cyclization see: Zoller, T.; Uguen, D.; DeCian, A.; Fischer, J.; Sablé, S. Tetrahedron Lett. 1997, 38, 3409-3412. Shishido, K.; Omodani, T.; Shibuya, M. J. Chem. Soc., Perkin Trans. 1 1991, 2285-2287. Shing, T. K. M.; Tang, Y. Tetrahedron 1990, 46, 2187-2194.
41. For recent examples of the IMDA cyclization with a gemdimethyl on the diene see: (a) Bonnert, R. V.; Jenkins, P. J. Chem. Soc., Perkin Trans. 1 1989, 413-418. (b) Rubenstein, S. M.; Williams, R. M. J. Org. Chem. 1995, 60, 7215-7223. (c) alaima, C. A.; Coburn, C. A.; Danishefsky, S. J. Tetrahedron Lett. 1994, 35, 6603-6606, and references therein. (d) Gwaltney, S. L. II; Sakata, S. T.; Shea, K. J. Tetrahedron Lett. 1995, 36, 7177-7180 and references therein. (e) Winkler, J. D.; Kim, H. S.; Kim, S. Ando, K.; Houk, K. N. J. Org. Chem. 1997, 62, 2957-2962.
42. For recent examples of the IMDA cyclization with a gemdimethyl on the diene see: (a) Bonnert, R. V.; Jenkins, P. J. Chem. Soc., Perkin Trans. 1 1989, 413-418. (b) Rubenstein, S. M.; Williams, R. M. J. Org. Chem. 1995, 60, 7215-7223. (c) alaima, C. A.; Coburn, C. A.; Danishefsky, S. J. Tetrahedron Lett. 1994, 35, 6603-6606, and references therein. (d) Gwaltney, S. L. II; Sakata, S. T.; Shea, K. J. Tetrahedron Lett. 1995, 36, 7177-7180 and references therein. (e) Winkler, J. D.; Kim, H. S.; Kim, S. Ando, K.; Houk, K. N. J. Org. Chem. 1997, 62, 2957-2962.
43. For recent examples of the IMDA cyclization with a gemdimethyl on the diene see: (a) Bonnert, R. V.; Jenkins, P. J. Chem. Soc., Perkin Trans. 1 1989, 413-418. (b) Rubenstein, S. M.; Williams, R. M. J. Org. Chem. 1995, 60, 7215-7223. (c) alaima, C. A.; Coburn, C. A.; Danishefsky, S. J. Tetrahedron Lett. 1994, 35, 6603-6606, and references therein. (d) Gwaltney, S. L. II; Sakata, S. T.; Shea, K. J. Tetrahedron Lett. 1995, 36, 7177-7180 and references therein. (e) Winkler, J. D.; Kim, H. S.; Kim, S. Ando, K.; Houk, K. N. J. Org. Chem. 1997, 62, 2957-2962.
44. For recent examples of the IMDA cyclization with a gemdimethyl on the diene see: (a) Bonnert, R. V.; Jenkins, P. J. Chem. Soc., Perkin Trans. 1 1989, 413-418. (b) Rubenstein, S. M.; Williams, R. M. J. Org. Chem. 1995, 60, 7215-7223. (c) alaima, C. A.; Coburn, C. A.; Danishefsky, S. J. Tetrahedron Lett. 1994, 35, 6603-6606, and references therein. (d) Gwaltney, S. L. II; Sakata, S. T.; Shea, K. J. Tetrahedron Lett. 1995, 36, 7177-7180 and references therein. (e) Winkler, J. D.; Kim, H. S.; Kim, S. Ando, K.; Houk, K. N. J. Org. Chem. 1997, 62, 2957-2962.
45. For recent examples of the IMDA cyclization with a gemdimethyl on the diene see: (a) Bonnert, R. V.; Jenkins, P. J. Chem. Soc., Perkin Trans. 1 1989, 413-418. (b) Rubenstein, S. M.; Williams, R. M. J. Org. Chem. 1995, 60, 7215-7223. (c) alaima, C. A.; Coburn, C. A.; Danishefsky, S. J. Tetrahedron Lett. 1994, 35, 6603-6606, and references therein. (d) Gwaltney, S. L. II; Sakata, S. T.; Shea, K. J. Tetrahedron Lett. 1995, 36, 7177-7180 and references therein. (e) Winkler, J. D.; Kim, H. S.; Kim, S. Ando, K.; Houk, K. N. J. Org. Chem. 1997, 62, 2957-2962.
46. Suffert, J.; Toussaint; D. J. Org. Chem. 1995, 60, 3550-3553.
47. The author has deposited atomic coordinates for 22b with the Cambridge Crystallographic Data Centre. The coordinates can be obtained from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK.
48. For reviews see: Yamamoto, Y.; Muruyama, K. J. Am. Chem. Soc. 1977, 99, 947-1038. Yamamoto, Y.; Ibuka, T. In Organocopper Reagents; Taylor, R. J. K., Ed.; Oxford University Press: Oxford, 1994; pp 143-158.
49. For reviews see: Yamamoto, Y.; Muruyama, K. J. Am. Chem. Soc. 1977, 99, 947-1038. Yamamoto, Y.; Ibuka, T. In Organocopper Reagents; Taylor, R. J. K., Ed.; Oxford University Press: Oxford, 1994; pp 143-158.