Total synthesis of bryostatin 2

Journal of the American Chemical Society

Volumn 121, Issue 33, 1999, Pages 7540-7552

  Evans, David A ^a   Carter, Percy H ^a   Carreira, Erick M ^a,b   Charette, André B ^a,c   Prunet, Joëlle A ^a,d   Lautens, Mark ^a,e  

^a HARVARD UNIVERSITY   (United States)

^b ETH ZURICH   (Switzerland)

^c UNIVERSITÉ DE MONTRÉAL   (Canada)

^d LABORATOIRE DE SYNTHÈSE ORGANIQUE   (France)

^e UNIVERSITY OF TORONTO   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

BRYOSTATIN 2;

ANTINEOPLASTIC ACTIVITY; ARTICLE; DRUG SYNTHESIS; MARINE ENVIRONMENT; POLYMERIZATION; REDUCTION;

EID: 0033603858     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja990860j     Document Type: Article

References (187)

1. Review: Pettit, G. R. The Bryostatins. In Progress in the Chemistry of Organic Natural Products; Herz, W., Ed.; Springer-Verlag: New York, 1991; No. 57, pp 153-195.
2. (a) Evans, D. A. Aldrichim. Acta 1982, 15, 23-32.
3. (b) Evans, D. A.; Kim, A. S. (S)-4-Benzyl-2-oxazolidinone. In Encyclopedia of Reagents for Organic Synthesis; Paquette, L. A., Editor-in-Chief; John Wiley and Sons: New York, 1995; Vol. 1, pp 345-356.
4. (c) Kim, A. S. Ph.D. Thesis, Harvard University, 1997.
5. -6% yield (18 g of bryostatin from 14 000 kg of animal) on industrial scale. Schaufelberger, D. E.; Koleck, M. P.; Beutler, J. A.; Vatakis, A. M.; Alvarado, A. B.; Andrews, P.; Marzo, L. V.; Muschik, G. M.; Roach, J.; Ross, J. T.; Lebherz, W. B.; Reeves, M. P.; Eberwein, R. M.; Rodgers, L. I.; Testerman, R. P.; Snader, K. M.; Forenza, S. J. Nat. Prod. 1991, 54, 1265-1270. (b) The current market price for bryostatin 1 is $1156 (U.S.)/500 μg: LC Laboratories, Woburn, MA.
6. (c) Marine aquaculture methods are currently being implemented in an attempt to solve the supply problem; cf. New Scientist 1996, 14 Sept, 38-42.
7. This work has been communicated in preliminary form: Evans, D. A.; Carter, P. H.; Carreira, E. M.; Prunet, J. A.; Charette, A. B.; Lautens, M. Angew. Chem., Int. Ed. 1998, 37, 2354-2359.
8. Pettit, G. R.; Herald, C. L.; Kamano, Y.; Gust, D.; Aoyagi, R. J. Nat. Prod. 1983, 46, 528-531.
9. Pettit has previously described the conversion of bryostatin 2 (1b) into bryostatin 1 (1a), cf.: Pettit, G. R.; Sengupta, D.; Herald, C. L.; Sharkey, N. A.; Blumberg, P. M. Can. J. Chem. 1991, 69, 856-860.
10. (a) Pettit, G. R.; Day, J. F.; Hartwell, J. L.; Wood, H. B. Nature 1970, 227, 962-963.
11. (b) Pettit, G. R.; Herald, C. L.; Doubek, D. L.; Herald, D. L.; Arnold, E.; Clardy, J. J. Am. Chem. Soc. 1982, 104, 6846-6848.
12. 13C NMR assignments of bryostatin 1, cf.: Schaufelberger, D. E.; Chmurny, G. N.; Koleck, M. P. Magn. Reson. Chem. 1991, 29, 366-374.
13. Engel, D. W. Acta Crystallogr., Sect. B 1972, B28, 1498-1509.
14. Pettit, G. R.; Herald, D. L.; Gao, F.; Sengupta, D.; Herald, C. L. J. Org. Chem. 1991, 56, 1337-1340.
15. Kamano, Y.; Zhang, H.; Morita, H.; Itokawa, H.; Shirota, O.; Pettit, G. R.; Herald, D. L.; Herald, C. L. Tetrahedron 1996, 52, 2369-2376.
16. Reviews: (a) Kraft, A. S. J. Natl. Cancer Inst. 1993, 85, 1790-1792. (b) Pettit, G. R. J. Nat. Prod. 1996, 59, 812-821. (c) Stone, R. M. Leukemia Res. 1997, 21, 399-401. (d) Information on the status of bryostatin clinical trials may be accessed via the Internet at http:// cancernet.nci.nih.gov/prot/protsrch.shtml.
17. Reviews: (a) Kraft, A. S. J. Natl. Cancer Inst. 1993, 85, 1790- 1792. (b) Pettit, G. R. J. Nat. Prod. 1996, 59, 812-821. (c) Stone, R. M. Leukemia Res. 1997, 21, 399-401. (d) Information on the status of bryostatin clinical trials may be accessed via the Internet at http:// cancernet.nci.nih.gov/prot/protsrch.shtml.
18. Reviews: (a) Kraft, A. S. J. Natl. Cancer Inst. 1993, 85, 1790- 1792. (b) Pettit, G. R. J. Nat. Prod. 1996, 59, 812-821. (c) Stone, R. M. Leukemia Res. 1997, 21, 399-401. (d) Information on the status of bryostatin clinical trials may be accessed via the Internet at http:// cancernet.nci.nih.gov/prot/protsrch.shtml.
19. Reviews: (a) Kraft, A. S. J. Natl. Cancer Inst. 1993, 85, 1790- 1792. (b) Pettit, G. R. J. Nat. Prod. 1996, 59, 812-821. (c) Stone, R. M. Leukemia Res. 1997, 21, 399-401. (d) Information on the status of bryostatin clinical trials may be accessed via the Internet at http:// cancernet.nci.nih.gov/prot/protsrch.shtml.
20. Schuchter, L. M.; Esa, A. H.; May, W.; Laulis, M. K.; Pettit, G. R.; Hess, A. D. Cancer Res. 1991, 51, 682-687.
21. (a) Trenn, G.; Pettit, G. R.; Takayama, H.; Hu-Li, J.; Sitkovsky, M. V. J. Immunol. 1988, 140, 433-439.
22. (b) Hess, A. D.; Silanksis, M. K.; Esa, A. H.; Pettit, G. R.; May, W. S. J. Immunol. 1988, 141, 3263-3269.
23. (c) Tuttle, T. M.; Inge, T. H.; Bethke, K. P.; McCrady, C. W.; Pettit, G. R.; Bear, H. D. Cancer Res. 1992, 52, 548-553.
24. (d) Mohr, H.; Pettit, G. R.; Plessing-Menze, A. Immunobiology 1987, 175, 420.
25. (e) Drexler, H. G.; Gignac, S. M.; Pettit, G. R.; Hoffbrand, A. V. Eur. J. Immunol. 1990, 20, 119-127.
26. (a) Tallant, E. A.; Smith, J. B.; Wallace, R. W. Biochim, Biophys. Acta 1987, 929, 40-46.
27. (b) May, W. S.; Sharkis, S. J.; Esa, A. H.; Gebbia, V.; Kraft, A. S.; Pettit, G. R.; Sensenbrenner, L. L. Proc. Natl. Acad. Sci. U.S.A. 1987, 84, 8483-8487.
28. (c) Grant, S.; Pettit, G. R.; McCrady, C. Exp. Hematol. 1992, 20, 34-42.
29. (d) Leonard, J. P.; May, W. S.; Ihle, J. N.; Pettit, G. R.; Sharkis, S. J. Blood 1988, 72, 1492-1496.
30. (e) Sharkis, S. J.; Jones, R. J.; Bellis, M. L.; Demetri, G. D.; Griffin, J. D.; Civin, C.; May, W. S. Blood 1990, 76, 716-720.
31. (f) McCrady, C. W.; Staniswalis, J.; Pettit, G. R.; Howe, C.; Grant, S. Br. J. Haematol. 1991, 77, 5-15.
32. (a) Smith, J. B.; Smith, L.; Pettit, G. R. Biochem. Biophys. Res. Commun. 1985, 132, 939-945.
33. (b) Berkow, R. L.; Kraft, A. S. Biochem. Biophys. Res. Commun. 1985, 131, 1109-1116.
34. (c) DeVries, D. J.; Herald, C. L.; Pettit, G. R.; Blumberg, P. M. Biochem. Pharm. 1988, 37, 4069-4073.
35. Hennings, H.; Blumberg, P. M.; Pettit, G. R.; Herald, C. L.; Shores, R.; Yuspa, S. Carcinogenesis 1987, 8, 1343-1346.
36. It should be noted that 12-deoxy-13-acyl phorbol esters also bind to PKC and induce an antitumor response. As with the bryostatins, a mechanism for this discrepancy is under investigation, cf.: Szallasi, Z.; Krsmanovi, L.; Blumberg, P. M. Cancer Res. 1993, 53, 2507-2512.
37. (a) Prendiville, J.; Crowther, D.; Thatcher, N.; Woll, P. J.; Fox, B. W.; McGown, A.; Testa, N.; Stern, P.; McDermott, R.; Potter, M.; Pettit, G. R. Br. J. Cancer 1993, 68, 418-424.
38. (b) Philip, P. A.; Rea, D.; Thavasu, P.; Carmichael, J.; Stuart, N. S. A.; Rockett, H.; Talbot, D. C.; Ganesan, T.; Pettit, G. R.; Balkwill, F.; Harris, A. L. J. Natl. Cancer Inst. 1993, 85, 1812-1818.
39. (c) Scheid, J.; Prendiville, J.; Jayson, G.; Crowther, D.; Fox, B.; Pettit, G. R. Cancer Immunol. Immunother. 1994, 39, 223-230.
40. (d) Jayson, G. C.; Crowther, D.; Prendiville, J.; McGown, A. T.; Scheid, C.; Stern, P.; Young, R.; Brenchley, P.; Chang, J.; Owens, S.; Pettit, G. R. Br. J. Cancer 1995, 72, 461-468.
41. (e) Varterasian, M. L.; Mohammad, R. M.; Eilender, D. S.; Hulburd, K.; Rodriguez, D. H.; Pemberton, P. A.; Pluda, J. M.; Dan, M. D.; Pettit, G. R.; Chen, B. D.; Al-Katib, A. M. J. Clin. Oncol. 1998, 16, 56-62.
42. (f) Grant, S.; Roberts, J.; Poplin, E.; Tombes, M. B.; Kyle, B.; Welch, D.; Carr, M.; Bear, H. D. Clin. Cancer Res. 1944, 4, 611-618.
43. (a) McGown, A. T.; Jayson, G.; Pettit, G. R.; Haran, M. S.; Ward, T. H.; Crowther, D. Br. J. Cancer 1998, 77, 216-220.
44. (b) Koutcher, J. A.; Matei, C.; Zakian, K.; Ballon, D.; Schwartz, G. K. Proc. Am. Assoc. Cancer Res. 1998, 39, 191 (No. 1304).
45. For a detailed review of the literature prior to early 1995, cf.: Norcross, R. D.; Paterson, I. Chem. Rev. 1995, 95, 2041-2114.
46. Recent work: (a) Kiyooka, S.; Maeda, H. Tetrahedron: Asymmetry 1997, 8, 3371-3374. (b) Weiss, J. M.; Hoffmann, H. M. R. Tetrahedron: Asymmetry 1997, 8, 3913-3920. (c) DeBrabander, J.; Kulkarni, B. A.; Garcia-Lopez, R.; Vandewalle, M. Tetrahedron: Asymmetry 1997, 8, 1721- 1724. (d) Lampe, T. F. J.; Hoffmann, H. M. R. Tetrahedron Lett. 1996, 37, 7695-7698. (e) Lampe, T. F. J.; Hoffmann, H. M. R. Chem. Commun. 1996, 1931-1932. (f) De Brabander, J.; Vandewalle, M. Pure Appl. Chem. 1996, 68, 715-718. (g) Kalesse, M.; Eh, M. Tetrahedron Lett. 1996, 37, 1767-1770. (h) Ohmori, K.; Suzuki, T.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6515-6518. (i) Ohmori, K.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6519-6522. (j) Hoffmann, R. W.; Stiasny, H. C. Tetrahedron Lett. 1995, 36, 4595-4598.
47. Recent work: (a) Kiyooka, S.; Maeda, H. Tetrahedron: Asymmetry 1997, 8, 3371-3374. (b) Weiss, J. M.; Hoffmann, H. M. R. Tetrahedron: Asymmetry 1997, 8, 3913-3920. (c) DeBrabander, J.; Kulkarni, B. A.; Garcia-Lopez, R.; Vandewalle, M. Tetrahedron: Asymmetry 1997, 8, 1721- 1724. (d) Lampe, T. F. J.; Hoffmann, H. M. R. Tetrahedron Lett. 1996, 37, 7695-7698. (e) Lampe, T. F. J.; Hoffmann, H. M. R. Chem. Commun. 1996, 1931-1932. (f) De Brabander, J.; Vandewalle, M. Pure Appl. Chem. 1996, 68, 715-718. (g) Kalesse, M.; Eh, M. Tetrahedron Lett. 1996, 37, 1767-1770. (h) Ohmori, K.; Suzuki, T.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6515-6518. (i) Ohmori, K.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6519-6522. (j) Hoffmann, R. W.; Stiasny, H. C. Tetrahedron Lett. 1995, 36, 4595-4598.
48. Recent work: (a) Kiyooka, S.; Maeda, H. Tetrahedron: Asymmetry 1997, 8, 3371-3374. (b) Weiss, J. M.; Hoffmann, H. M. R. Tetrahedron: Asymmetry 1997, 8, 3913-3920. (c) DeBrabander, J.; Kulkarni, B. A.; Garcia-Lopez, R.; Vandewalle, M. Tetrahedron: Asymmetry 1997, 8, 1721-1724. (d) Lampe, T. F. J.; Hoffmann, H. M. R. Tetrahedron Lett. 1996, 37, 7695-7698. (e) Lampe, T. F. J.; Hoffmann, H. M. R. Chem. Commun. 1996, 1931-1932. (f) De Brabander, J.; Vandewalle, M. Pure Appl. Chem. 1996, 68, 715-718. (g) Kalesse, M.; Eh, M. Tetrahedron Lett. 1996, 37, 1767-1770. (h) Ohmori, K.; Suzuki, T.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6515-6518. (i) Ohmori, K.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6519-6522. (j) Hoffmann, R. W.; Stiasny, H. C. Tetrahedron Lett. 1995, 36, 4595-4598.
49. Recent work: (a) Kiyooka, S.; Maeda, H. Tetrahedron: Asymmetry 1997, 8, 3371-3374. (b) Weiss, J. M.; Hoffmann, H. M. R. Tetrahedron: Asymmetry 1997, 8, 3913-3920. (c) DeBrabander, J.; Kulkarni, B. A.; Garcia-Lopez, R.; Vandewalle, M. Tetrahedron: Asymmetry 1997, 8, 1721- 1724. (d) Lampe, T. F. J.; Hoffmann, H. M. R. Tetrahedron Lett. 1996, 37, 7695-7698. (e) Lampe, T. F. J.; Hoffmann, H. M. R. Chem. Commun. 1996, 1931-1932. (f) De Brabander, J.; Vandewalle, M. Pure Appl. Chem. 1996, 68, 715-718. (g) Kalesse, M.; Eh, M. Tetrahedron Lett. 1996, 37, 1767-1770. (h) Ohmori, K.; Suzuki, T.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6515-6518. (i) Ohmori, K.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6519-6522. (j) Hoffmann, R. W.; Stiasny, H. C. Tetrahedron Lett. 1995, 36, 4595-4598.
50. Recent work: (a) Kiyooka, S.; Maeda, H. Tetrahedron: Asymmetry 1997, 8, 3371-3374. (b) Weiss, J. M.; Hoffmann, H. M. R. Tetrahedron: Asymmetry 1997, 8, 3913-3920. (c) DeBrabander, J.; Kulkarni, B. A.; Garcia-Lopez, R.; Vandewalle, M. Tetrahedron: Asymmetry 1997, 8, 1721- 1724. (d) Lampe, T. F. J.; Hoffmann, H. M. R. Tetrahedron Lett. 1996, 37, 7695-7698. (e) Lampe, T. F. J.; Hoffmann, H. M. R. Chem. Commun. 1996, 1931-1932. (f) De Brabander, J.; Vandewalle, M. Pure Appl. Chem. 1996, 68, 715-718. (g) Kalesse, M.; Eh, M. Tetrahedron Lett. 1996, 37, 1767-1770. (h) Ohmori, K.; Suzuki, T.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6515-6518. (i) Ohmori, K.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6519-6522. (j) Hoffmann, R. W.; Stiasny, H. C. Tetrahedron Lett. 1995, 36, 4595-4598.
51. Recent work: (a) Kiyooka, S.; Maeda, H. Tetrahedron: Asymmetry 1997, 8, 3371-3374. (b) Weiss, J. M.; Hoffmann, H. M. R. Tetrahedron: Asymmetry 1997, 8, 3913-3920. (c) DeBrabander, J.; Kulkarni, B. A.; Garcia-Lopez, R.; Vandewalle, M. Tetrahedron: Asymmetry 1997, 8, 1721- 1724. (d) Lampe, T. F. J.; Hoffmann, H. M. R. Tetrahedron Lett. 1996, 37, 7695-7698. (e) Lampe, T. F. J.; Hoffmann, H. M. R. Chem. Commun. 1996, 1931-1932. (f) De Brabander, J.; Vandewalle, M. Pure Appl. Chem. 1996, 68, 715-718. (g) Kalesse, M.; Eh, M. Tetrahedron Lett. 1996, 37, 1767-1770. (h) Ohmori, K.; Suzuki, T.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6515-6518. (i) Ohmori, K.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6519-6522. (j) Hoffmann, R. W.; Stiasny, H. C. Tetrahedron Lett. 1995, 36, 4595-4598.
52. Recent work: (a) Kiyooka, S.; Maeda, H. Tetrahedron: Asymmetry 1997, 8, 3371-3374. (b) Weiss, J. M.; Hoffmann, H. M. R. Tetrahedron: Asymmetry 1997, 8, 3913-3920. (c) DeBrabander, J.; Kulkarni, B. A.; Garcia-Lopez, R.; Vandewalle, M. Tetrahedron: Asymmetry 1997, 8, 1721- 1724. (d) Lampe, T. F. J.; Hoffmann, H. M. R. Tetrahedron Lett. 1996, 37, 7695-7698. (e) Lampe, T. F. J.; Hoffmann, H. M. R. Chem. Commun. 1996, 1931-1932. (f) De Brabander, J.; Vandewalle, M. Pure Appl. Chem. 1996, 68, 715-718. (g) Kalesse, M.; Eh, M. Tetrahedron Lett. 1996, 37, 1767-1770. (h) Ohmori, K.; Suzuki, T.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6515-6518. (i) Ohmori, K.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6519-6522. (j) Hoffmann, R. W.; Stiasny, H. C. Tetrahedron Lett. 1995, 36, 4595-4598.
53. Recent work: (a) Kiyooka, S.; Maeda, H. Tetrahedron: Asymmetry 1997, 8, 3371-3374. (b) Weiss, J. M.; Hoffmann, H. M. R. Tetrahedron: Asymmetry 1997, 8, 3913-3920. (c) DeBrabander, J.; Kulkarni, B. A.; Garcia-Lopez, R.; Vandewalle, M. Tetrahedron: Asymmetry 1997, 8, 1721- 1724. (d) Lampe, T. F. J.; Hoffmann, H. M. R. Tetrahedron Lett. 1996, 37, 7695-7698. (e) Lampe, T. F. J.; Hoffmann, H. M. R. Chem. Commun. 1996, 1931-1932. (f) De Brabander, J.; Vandewalle, M. Pure Appl. Chem. 1996, 68, 715-718. (g) Kalesse, M.; Eh, M. Tetrahedron Lett. 1996, 37, 1767-1770. (h) Ohmori, K.; Suzuki, T.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6515-6518. (i) Ohmori, K.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6519-6522. (j) Hoffmann, R. W.; Stiasny, H. C. Tetrahedron Lett. 1995, 36, 4595-4598.
54. Recent work: (a) Kiyooka, S.; Maeda, H. Tetrahedron: Asymmetry 1997, 8, 3371-3374. (b) Weiss, J. M.; Hoffmann, H. M. R. Tetrahedron: Asymmetry 1997, 8, 3913-3920. (c) DeBrabander, J.; Kulkarni, B. A.; Garcia-Lopez, R.; Vandewalle, M. Tetrahedron: Asymmetry 1997, 8, 1721- 1724. (d) Lampe, T. F. J.; Hoffmann, H. M. R. Tetrahedron Lett. 1996, 37, 7695-7698. (e) Lampe, T. F. J.; Hoffmann, H. M. R. Chem. Commun. 1996, 1931-1932. (f) De Brabander, J.; Vandewalle, M. Pure Appl. Chem. 1996, 68, 715-718. (g) Kalesse, M.; Eh, M. Tetrahedron Lett. 1996, 37, 1767-1770. (h) Ohmori, K.; Suzuki, T.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6515-6518. (i) Ohmori, K.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6519-6522. (j) Hoffmann, R. W.; Stiasny, H. C. Tetrahedron Lett. 1995, 36, 4595-4598.
55. Recent work: (a) Kiyooka, S.; Maeda, H. Tetrahedron: Asymmetry 1997, 8, 3371-3374. (b) Weiss, J. M.; Hoffmann, H. M. R. Tetrahedron: Asymmetry 1997, 8, 3913-3920. (c) DeBrabander, J.; Kulkarni, B. A.; Garcia-Lopez, R.; Vandewalle, M. Tetrahedron: Asymmetry 1997, 8, 1721- 1724. (d) Lampe, T. F. J.; Hoffmann, H. M. R. Tetrahedron Lett. 1996, 37, 7695-7698. (e) Lampe, T. F. J.; Hoffmann, H. M. R. Chem. Commun. 1996, 1931-1932. (f) De Brabander, J.; Vandewalle, M. Pure Appl. Chem. 1996, 68, 715-718. (g) Kalesse, M.; Eh, M. Tetrahedron Lett. 1996, 37, 1767-1770. (h) Ohmori, K.; Suzuki, T.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6515-6518. (i) Ohmori, K.; Nishiyama, S.; Yamamura, S. Tetrahedron Lett. 1995, 36, 6519-6522. (j) Hoffmann, R. W.; Stiasny, H. C. Tetrahedron Lett. 1995, 36, 4595-4598.
56. (a) Evans, D. A.; Gauchet-Prunet, J. A.; Carreira, E. M.; Charette, A. B. J. Org. Chem. 1991, 56, 741-750.
57. (b) Evans, D. A.; Carreira, E. M. Tetrahedron Lett. 1990, 31, 4703-4706.
58. (c) Evans, D. A.; Carreira, E. M.; Charette, A. B.; Gauchet, J. A. Abstracts of Papers, 196th National Meeting of the American Chemical Society, Los Angeles, CA, Fall 1998; American Chemical Society: Washington, DC, 1988; ORGN 209.
59. (a) Kageyama, M.; Tamura, T.; Nantz, M. H.; Roberts, J. C.; Somfai, P.; Whritenour, D. C.; Masamune, S. J. Am. Chem. Soc. 1990, 112, 7407-7408.
60. (b) Blanchette, M. A.; Malamas, M. S.; Nantz, M. H.; Roberts, J. C.; Somfai, P.; Whritenour, D. C.; Masamune, S.; Kageyama, M.; Tamura, T. J. Org. Chem. 1989, 54, 2817-2825.
61. (c) Masamune, S. Pure Appl. Chem. 1988, 60, 1587-1596.
62. (a) Bartra, M.; Urpí, F.; Vilarrasa, J. In Recent Progress in the Chemical Synthesis of Antibiotics and Related Microbial Products; Lukacs, G., Ed.; Springer-Verlag: Berlin, 1993; Vol. 2.
63. (b) Boeckman, R. K.; Goldstein, S. W. In The Total Synthesis of Natural Products; Apsimon, J., Ed.; Wiley: New York, 1988; Vol. 7, pp 1-139.
64. (c) Paterson, I.; Mansuri, M. M. Tetrahedron 1985, 41, 3569-3624.
65. (a) Ley, S. V.; Lygo, B.; Sternfeld, F.; Wonnacott, A. Tetrahedron 1986, 42, 4333-4342.
66. (b) For a description of the development of this methodology, cf.: Ley, S. V.; Armstrong, A. In Strategies and Tactics in Organic Synthesis; Lindberg, T., Ed.; Academic Press: San Diego, 1991; Vol. 3, pp 237-292.
67. (a) Julia, M.; Paris, J. M. Tetrahedron Lett. 1973, 4833-4836.
68. (b) Kocienski, P. J.; Lythgoe, B.; Ruston, S. J. Chem. Soc., Perkin Trans. 1 1978, 829.
69. (c) Review: Kocienski, P. Phosphorus Sulfur 1985, 24, 97-127.
70. Kerr, R. G.; Lawry, J.; Gush, K. A. Tetrahedron Lett. 1996, 37, 8305-8308.
71. (a) Evans, D. A.; Chapman, K. T.; Carreira, E. M. J. Am. Chem. Soc. 1988, 110, 3560-3578.
72. (b) Evans, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1990, 112, 6447-6449.
73. Evans, D. A.; Kozlowski, M. C.; Murry, J. A.; Burgey, C. S.; Campos, K. R.; Connell, B. T.; Staples, R. J. J. Am. Chem. Soc. 1999, 121, 669-685.
74. Gao, R.; Hanson, J.; Klunder, J. M.; Ko, S. Y.; Masamune, H.; Sharpless, K. B. J. Am. Chem. Soc. 1987, 109, 5765-5780.
75. (a) Evans, D. A.; Coleman, P. J.; Côté, B. J. Org. Chem. 1997, 62, 788-789.
76. (b) Lagu, B. R.; Liotta, D. C. Tetrahedron Lett. 1994, 35, 4485-4488.
77. (c) Trost, B. M.; Urabe, H. J. Org. Chem. 1990, 55, 3982-3983.
78. (d) Paterson, I.; Goodman, J. M.; Isaka, M. Tetrahedron Lett. 1989, 30, 7121-7124.
79. Evans, D. A.; Dart, M. J.; Duffy, J. L.; Yang, M. G. J. Am. Chem. Soc. 1996, 118, 4322-4343 and references therein.
80. For a discussion of the earlier approaches based on the epoxystyrene synthon strategy, cf.: (a) Carreira, E. M. Ph.D. Thesis, Harvard University, 1990. (b) Gauchet-Prunet, J. A. Ph.D. Thesis, Harvard University, 1993.
81. For a discussion of the earlier approaches based on the epoxystyrene synthon strategy, cf.: (a) Carreira, E. M. Ph.D. Thesis, Harvard University, 1990. (b) Gauchet-Prunet, J. A. Ph.D. Thesis, Harvard University, 1993.
82. Evans, D. A.; Carter, P. H.; Dinsmore, C. J.; Barrow, J. C.; Katz, J. L.; Kung, D. W. Tetrahedron Lett. 1997, 38, 4535-4538.
83. Evans, D. A.; Sjogren, E. B.; Weber, A. E.; Conn, R. E. Tetrahedron Lett. 1987, 28, 39-42.
84. (a) Julia, M.; Baillarge, M. Bull. Soc. Chim. Fr. 1966, 734-742.
85. (b) Zimmerman, H. E.; Pratt, A. C. J. Am. Chem. Soc. 1970, 92, 6259-6267.
86. Penning, T. D.; Djuric, S. W.; Haack, R. A.; Kalish, V. J.; Miyashiro, J. M.; Rowell, B. W.; Yu, S. S. Synth. Commun. 1990, 20, 307-312.
87. (a) Johansson, R.; Samuelsson, B. J. Chem. Soc., Chem. Commun. 1984, 201.
88. (b) Johansson, R.; Samuelsson, B. J. Chem. Soc., Perkin Trans. 1 1984, 2371-2374.
89. 1H NMR NOE analysis of sulfone 8.
90. 1H NMR NOE analysis of lactone 18.
91. 2, 50% yield, unoptimized).
92. 9 olefin. With the lactone 18, where the TBS ether is conformationally constrained and the PMB ether can rotate away from the olefin (MM2), no epoxidation was observed. This product aldehyde could not be advanced to 20.
93. (a) Hanessian, S.; Guindon, Y. Carbohydr. Res. 1980, 86, C3.
94. (b) Nicolaou, K. C.; Daines, R. A.; Ogawa, Y.; Chakraborty, T. K. J. Am. Chem. Soc. 1988, 110, 4696-4705.
95. (c) Evans, D. A.; Truesdale, L. K.; Grimm, K. G.; Nesbitt, S. L. J. Am. Chem. Soc. 1977, 99, 5099-5116.
96. 7 p-methoxybenzoate impurity were removed at this stage by flash chromatography.
97. Still, W. C. J. Am. Chem. Soc. 1978, 100, 1481-1486.
98. ax. Given the propensity for lactols to equilibrate in aqueous media, this stereochemistry may arise from a postaddition isomerization, cf.: Dondoni, A.; Schurmann, M.-C. J. Org. Chem. 1994, 59, 6404-6412.
99. Lewis, M. D.; Cha, J. K.; Kishi, Y. J. Am. Chem. Soc. 1982, 104, 4976-4978.
100. 14).
101. 10 PMB ether.
102. 3, 23°C, 90 min. (70:30 E:Z); KHMDS, THF, 0°C, 30 min. (50:50 E:Z). (b) Recent results from the laboratory of H. M. R. Hoffmann indicate that the exocyclic ethyl ester may be installed in good stereoselectivity (9:1 E:Z, 72% yield); cf. ref 24e.
103. Blanchette, M. A.; Choy, W.; Davis, J. T.; Essenfeld, A. P.; Masamune, S.; Roush, W. R.; Sakai, T. Tetrahedron Lett. 1984, 25, 2183-2186.
104. 12 equatorial proton. The opposite deshielding pattern was seen for the Z isomer.
105. For leading references to the recent literature, cf.: (a) Abiko, A.; Masamune, S. Tetrahedron Lett. 1996, 37, 1077-1080. (b) Denmark, S. E.; Rivera, I. J. Org. Chem. 1994, 59, 6887-6889.
106. For leading references to the recent literature, cf.: (a) Abiko, A.; Masamune, S. Tetrahedron Lett. 1996, 37, 1077-1080. (b) Denmark, S. E.; Rivera, I. J. Org. Chem. 1994, 59, 6887-6889.
107. (a) Tanaka, K.; Ohta, Y.; Fuji, K.; Taga, T. Tetrahedron Lett. 1993, 34, 4071-4074.
108. (b) Tanaka, K.; Otsubo, K.; Fuji, K. Tetrahedron Lett. 1996, 37, 3735-3738.
109. 3, and THF/HMPA), and temperature (0, -35, -65, and -78°C).
110. (a) The reaction of either 35a or 35b with dihydrocinnamaldehyde (NaHMDS, THF, -78°C) afforded an 82:18 Z:E mixture of olefins. (b) The Z stereoselectivity of achiral phenolic phosphonates with simple aldehydes has recently been documented, cf.: Ando, K. J. Org. Chem. 1997, 62, 1934-1939.
111. For discussions regarding the mechanism of the Horner-Wadsworth-Emmons olefination, cf.: (a) Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 863. (b) Vedejs, E.; Peterson, M. J. Top. Stereochem. 1994, 21, 1-157.
112. For discussions regarding the mechanism of the Horner-Wadsworth-Emmons olefination, cf.: (a) Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 863. (b) Vedejs, E.; Peterson, M. J. Top. Stereochem. 1994, 21, 1-157.
113. Evans, D. A.; Kaldor, S. W.; Jones, T. K.; Clardy, J.; Stout, T. J. J. Am. Chem. Soc. 1990, 112, 7001-7031.
114. 19 carboxylic acid or Weinreb amide was low-yielding.
115. (a) Minato, M.; Yamamoto, K.; Tsuji, J. J. Org. Chem. 1990, 55, 766-768.
116. (b) Kolb, H. C.; VanNieuwenhze, M. S.; Sharpless, K. B. Chem. Rev. 1994, 94, 2483-2547.
117. (a) A study of the aldol reaction of 40 (and other protected variants: TBDPS, MEM, BOM, Bn) with propionaldehyde demonstrated that only moderate yields (25-50%) and low selectivities (<3:1 diastereoselection in the desired sense) could be obtained using a wide array of metal centers (Li, B, Sn, Zn, Mg, Ti) and enolization conditions, (b) For the obtainment of the undesired 1,4-syn diastereomer in high stereoselectivity, cf. ref 34c.
118. (a) Ramachandran, P. V.; Xu, W.-C.; Brown, H. C. Tetrahedron Lett. 1996, 37, 4911-4914.
119. (b) Paterson, I.; Goodman, J. M.; Lister, M. A.; Schumann, R. C.; McClure, C. K.; Norcross, R. D. Tetrahedron 1990, 46, 4663-4684.
120. DIPCl is a trademark of the Aldrich Chemical Co. (DIP = diisopinocampheyl).
121. Assuming a base level selectivity of 89:11 for the reaction of n-alkylaldehydes with these IPC enolates (ref 65b), our stereoselectivities are roughly in accord with the precepts for double diastereodifferentiation: calculated value = 8/1 × 2.2/1 = 17.8/1 ratio of S/R; actual value = 19/1; cf.: Masamune, S.; Choy, W.; Peterson, J. S.; Sita, L. R. Angew. Chem., Int. Ed. Engl. 1985, 24, 1-30.
122. 3) secured the stereochemical assignment for both the aldol and reduction steps.
123. 23 benzoate was too difficult to remove.
124. The use of N-methyl imidazolyl sulfones has been reported to improve the Julia olefination, cf.: Kende, A. S.; Mendoza, J. S. Tetrahedron Lett. 1990, 31, 7105-7108.
125. (a) Dess, D. B.; Martin, J. C. J. Am. Chem. Soc. 1991, 113, 7277-7287.
126. (b) For an improved preparation of the reagent, cf.: Ireland, R. E.; Liu, L. J. Org. Chem. 1993, 58, 2899.
127. 17 substituent.
128. Pettit, G.; Green, B.; Dunn, G. L. J. Org. Chem. 1970, 35, 1367-1376.
129. Reaction times longer than 20-30 min provided for considerably reduced yields because of olefin isomerization (E → Z).
130. Luche, J. L. J. Am. Chem. Soc. 1978, 100, 2226.
131. Subasinghe, N.; Schulte, M.; Chan, M. Y.-M.; Roon, R. J.; Koerner, J. F.; Johnson, R. L. J. Med. Chem. 1990, 33, 2734-2744.
132. (a) Jones, A. B.; Villalobos, A.; Linde, R. G.; Danishefsky, S. J. J. Org. Chem. 1990, 55, 2786.
133. (b) Evans, D. A.; Ng, H. P.; Rieger, D. L. J. Am. Chem. Soc. 1993, 115, 11446-11459.
134. eq were in accord with the assigned stereochemistry.
135. 2AlCl, THF, room temperature, 16 h, 96% yield).
136. 9 sulfonyl anions.
137. 9 lactol were obtained, indicating that the sulfinate elimination was slower than the anion alkylation.
138. This is consistent with the results of both Ley and Beau; cf. ref 28 and the following: Beau, J.-M.; Sinaÿ, P. Tetrahedron Lett. 1985, 26, 6189-6192.
139. The cyclopropane was isolated in 77% yield when the coupling was carried out in the absence of HMPA.
140. 9 ketal. For a discussion of amide hydrolysis, cf. ref 37.
141. Ketal 56 was completely unstable when stored neat and reverted back to the enol ether and lactols after even 10-30 min at room temperature. In contrast, the benzyl, PMB, and t-Bu amide analogues were perfectly stable, even after prolonged storage.
142. 2H quench. The avoidance of HMPA required that a higher temperature be utilized in the alkylation step.
143. 22 (data not shown).
144. 2 (Achmatowicz, B.; Baranowska, E.; Daniewski, A. R.; Pankowski, J.; Wicha, J. Tetrahedron 1988, 44, 4989).
145. 2 (Achmatowicz, B.; Baranowska, E.; Daniewski, A. R.; Pankowski, J.; Wicha, J. Tetrahedron 1988, 44, 4989).
146. 17.
147. 2 was used as the base.
148. 17-phenyl sulfone could be accomplished, the resultant anion (or modified variants thereof) proved to be more basic than nucleophilic.
149. For the use of both ylide and nitronate anions generated β to a THP oxygen, cf.: (a) McWhorter, W. W., Jr. Ph.D. Thesis, Harvard University, 1984. (b) Secrist, J. A., III; Wu, S.-R. J. Org. Chem. 1977, 42, 4084- 4088. (c) Kobertz, W. R.; Bertozzi, C. R.; Bednarski, M. D. J. Org. Chem. 1996, 61, 1894-1897. (d) Martin, O. R.; Lai, W. J. Org. Chem. 1990, 55, 5188.
150. For the use of both ylide and nitronate anions generated β to a THP oxygen, cf.: (a) McWhorter, W. W., Jr. Ph.D. Thesis, Harvard University, 1984. (b) Secrist, J. A., III; Wu, S.-R. J. Org. Chem. 1977, 42, 4084-4088. (c) Kobertz, W. R.; Bertozzi, C. R.; Bednarski, M. D. J. Org. Chem. 1996, 61, 1894-1897. (d) Martin, O. R.; Lai, W. J. Org. Chem. 1990, 55, 5188.
151. For the use of both ylide and nitronate anions generated β to a THP oxygen, cf.: (a) McWhorter, W. W., Jr. Ph.D. Thesis, Harvard University, 1984. (b) Secrist, J. A., III; Wu, S.-R. J. Org. Chem. 1977, 42, 4084- 4088. (c) Kobertz, W. R.; Bertozzi, C. R.; Bednarski, M. D. J. Org. Chem. 1996, 61, 1894-1897. (d) Martin, O. R.; Lai, W. J. Org. Chem. 1990, 55, 5188.
152. For the use of both ylide and nitronate anions generated β to a THP oxygen, cf.: (a) McWhorter, W. W., Jr. Ph.D. Thesis, Harvard University, 1984. (b) Secrist, J. A., III; Wu, S.-R. J. Org. Chem. 1977, 42, 4084- 4088. (c) Kobertz, W. R.; Bertozzi, C. R.; Bednarski, M. D. J. Org. Chem. 1996, 61, 1894-1897. (d) Martin, O. R.; Lai, W. J. Org. Chem. 1990, 55, 5188.
153. 2O, 2,6-lutidine, -10°C; (iv) LiSIm, THF, 0°C; (v) m-CPBA. See the Supporting Information for details.
154. For the use of LiBr with enolates, see: Seebach, D. Angew. Chem., Int. Ed. Engl. 1988, 27, 1624.
155. The sulfone anion decomposed slowly at -78°C, producing about 10% of ring-opened elimination product in 1 h. For comparison, the lithium anion of a related phenyl sulfone anion instantly produced the undesired open-chain product, cf.: Barnes, N. J.; Davidson, A. H.; Hughes, L. R.; Procter, G. J. Chem. Soc., Chem. Commun. 1985, 1292-1294.
156. 2, 5°C; (iii) Dess-Martin oxidation.
157. The hindered aldehyde 59 was unreactive toward a number of standard enolate nucleophiles but could be engaged with unhindered silyl enol ethers under Lewis acid catalysis. For the reaction of a similar C-ring aldehyde with an allylboronate, cf.: Wender, P. A.; DeBrabander, J.; Harran, P.; Jimenez, J.-M.; Koehler, M.; Lippa, B.; Park, C.-M. J. Am. Chem. Soc. 1998, 120, 4534-4535.
158. To obtain complete conversion, the addition step needed to be carried out at -50°C.
159. Lee, G. H.; Lee, H. K.; Choi, E. B.; Kim, B. T.; Pak, C. S. Tetrahedron Lett. 1995, 36, 5607-5610.
160. 10-OTBS. Less than 30% of the primary alcohol was isolated under a variety of acidic desilylation conditions.
161. The triflate 61 decomposed rapidly (<10 min) when left in neat form. See the Supporting Information for the details of the purification of 61.
162. In practice, the lactol 62 was obtained in 60-75% yield after chromatography. An additional 15-20% was isolated as the hydroxyketone tautomer, which was silylated (vide infra) to reconverge the material. See the Supporting Information for details.
163. Our earlier results with acidic methanolysis of the A and C ring enol ethers showed that the equilibrium lay on the side of either the ketal (A ring) or the enol ether (C ring), depending on the position (exo or endo) and steric environment of the enol ether.
164. a of N-phenyl acetamide, cf.: Bordwell, F. G. Acc. Chem. Res. 1988, 21, 456-463.
165. Evans, D. A.; Ennis, M. D.; Mathre, D. J. J. Am. Chem. Soc. 1982, 104, 1737-1739.
166. Jacobi has observed that DMF improves the ratio of exocyclic to endocyclic cleavage in the LiOOH-mediated hydrolysis of N-acyloxazolidinones, cf.: Jacobi, P. A.; Murphee, S.; Rupprecht, F.; Zheng, W. J. Org. Chem. 1996, 61, 2413-2427.
167. Interestingly, the less basic magnesio species (MgOBn, BnOH) also inhibited the elimination reaction but resulted in the wrong cleavage regioselectivity (the anilide 65 was the major product).
168. Only the final product 67 was purified via flash chromatography.
169. For another use of HF-Pyr/MeOH with a mixed methyl ketal, cf.: Nicolaou, K. C.; Daines, R. A.; Ogawa, Y.; Chakraborty, T. K. J. Am. Chem. Soc. 1988, 110, 4696-4705.
170. The best result obtained with the carboxylic acid derivative of 68 (R = R′ = H) utilized the thiopyridyl ester (cf. Corey, E. J.; Nicolaou, K. C. J. Am. Chem. Soc. 1974, 96, 5614-5616) and provided the macrocycle in 14% yield for the two steps (thioester formation and cyclization).
171. Felix, A. M.; Heimer, E. P.; Lambros, T. J.; Tzougraki, C.; Meienhofer, J. J. Org. Chem. 1978, 43, 4194-4196.
172. (a) Evans, D. A.; Kim, A. S. J. Am. Chem. Soc. 1996, 118, 11323-11324.
173. (b) Inanaga, J.; Hirata, K.; Saeki, H.; Katsuki, T.; Yamaguchi, M. Bull. Chim. Soc. Jpn. 1979, 52, 1989-1993.
174. 20 ketone is both sterically crowded and electronically deactivated. Model studies with the C-ring intermediate 49 showed that this ketone failed to react with the sodium anion of trimethylphosphonoacetate, even over the course of several days.
175. eq resonance in the NOESY spectrum of 73.
176. 20 ketone.
177. (a) Ireland, R. E.; Gleason, J. L.; Gegnas, L. D.; Highsmith, T. K. J. Org. Chem. 1996, 61, 6856-6872.
178. (b) Ireland, R. E.; Wipf, P.; Armstrong, J. D., III. J. Org. Chem. 1991, 56, 650-657.
179. 3-OTES group.
180. 9 ketal had been a liability throughout the course of the synthesis, and all compounds (except 76) that contained this group had to be handled carefully in order to avoid spurious hydrolysis.
181. (a) Corey, E. J.; Bakshi, R. K.; Shibata, S.; Chen, C.-P.; Singh, V. K. J. Am. Chem. Soc. 1987, 109, 7925-7926.
182. (b) For a review, cf.: Corey, E. J.; Helal, C. J. Angew. Chem., Int. Ed. 1998, 37, 1986-2012. (c) Interestingly, the use of the B-Me catalyst was found to be superior to the B-Bu catalyst, presumably due to the large degree of steric crowding experienced in the transition state for the reduction. In addition, borane methyl sulfide was the only suitable hydride source for the reaction.
183. 34H.; and (iii) the synthesis of 1b and 1c (vide infra).
184. 3 hydroxyl group, that dictates the preferred solution conformation of the molecule. For a more detailed discussion, see: Carter, P. H. Ph.D. Thesis, Harvard University, 1998.
185. 1H NMR) completely consistent with those reported by Pettit et al.: Pettit, G. R.; Kamano, Y.; Herald, C. L.; Tozawa, M. Can. J. Chem. 1985, 63, 1204-1208.
186. For a completely different approach to analogue development, cf. the work of Wender et al.: (a) Wender, P. A.; DeBrabander, J.; Harran, P.; Jimenez, J.-M.; Koehler, M.; Lippa, B.; Park, C.-M. J. Am. Chem. Soc. 1998, 120, 4534-4535. (b) Wender, P. A.; DeBrabander, J.; Harran, P. G.; Jimenez, J.-M.; Koehler, M. F. T.; Lippa, B.; Park, C.-M.; Siedenbiedel, C.; Pettit, G. R. Proc. Natl. Acad. Sci. U.S.A. 1998, 95, 6624-6629.
187. For a completely different approach to analogue development, cf. the work of Wender et al.: (a) Wender, P. A.; DeBrabander, J.; Harran, P.; Jimenez, J.-M.; Koehler, M.; Lippa, B.; Park, C.-M. J. Am. Chem. Soc. 1998, 120, 4534-4535. (b) Wender, P. A.; DeBrabander, J.; Harran, P. G.; Jimenez, J.-M.; Koehler, M. F. T.; Lippa, B.; Park, C.-M.; Siedenbiedel, C.; Pettit, G. R. Proc. Natl. Acad. Sci. U.S.A. 1998, 95, 6624-6629.