Total synthesis of (+)-calyculin A and (-)-calyculin B: Cyanotetraene construction, asymmetric synthesis of the C(26-37) oxazole, fragment assembly, and final elaboration

Journal of the American Chemical Society

Volumn 121, Issue 45, 1999, Pages 10478-10486

  Smith III, Amos B ^a   Friestad, Gregory K ^a   Barbosa, Joseph ^a   Bertounesque, Emmanuel ^a   Duan, James J W ^a   Hull, Kenneth G ^a   Iwashima, Makoto ^a   Qiu, Yuping ^a   Spoors, P Grant ^a   Salvatore, Brian A ^a  

^a UNIVERSITY OF PENNSYLVANIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CALYCULIN A; CALYCULIN B; ENZYME INHIBITOR; MARINE TOXIN; NITRILE; OXAZOLE DERIVATIVE; PHOSPHATASE; PHOSPHONIC ACID DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; ENANTIOMER; NUCLEAR MAGNETIC RESONANCE; PHOTOSENSITIVITY; SYNTHESIS;

EID: 0033579151     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja992135e     Document Type: Article

References (75)

1. Part 1: Smith, A. B., III; Friestad, G. K.; Barbosa, J.; Bertounesque, E.; Hull, K. G.; Iwashima, M.; Qiu, Y.; Salvatore, B. A.; Spoors, P. G.; Duan, J. J.-W. J. Am. Chem. Soc. 1999, 121, XXXX.
2. At the start of our work, the absolute stereochemistry was unknown.
3. Matsunaga, S.; Fusetani, N. Tetrahedron Lett. 1991, 32, 5605.
4. (b) Hamada, Y.; Tanada, Y.; Yokokawa, F.; Shioiri, T. Tetrahedron Lett. 1991, 32, 5983.
5. Preliminary communications: (a) Smith, A. B., III; Friestad, G. K.; Duan, J. J.-W.; Barbosa, J.; Hull, K. G.; Iwashima, M.; Qiu, Y.; Spoors, P. G.; Bertounesque, E.; Salvatore, B. A. J. Org. Chem. 1998, 63, 7596. (b) Smith, A. B., III; Cho, Y. S.; Friestad, G. K. Tetrahedron Lett. 1998, 39, 8765. (c) Iwashima, M.; Kinsno, T.; Smith, A. B., III. Tetrahedron Lett. 1995, 36, 2199. (d) Smith, A. B., III; Iwashima, M. Tetrahedron Lett. 1994, 55, 6051. (e) Salvatore, B. A.; Smith, A. B., III. Tetrahedron Lett. 1994, 35, 1329. (f) Smith, A. B., III; Salvatore, B. A.; Hull, K. G.; Duan, J. J.-W. Tetrahedron Lett. 1991, 32, 4859. (g) Smith, A. B., III; Duan, J. J.-W.; Hull, K. G.; Salvatore, B. A. Tetrahedron Lett. 1991, 32, 4855.
6. Preliminary communications: (a) Smith, A. B., III; Friestad, G. K.; Duan, J. J.-W.; Barbosa, J.; Hull, K. G.; Iwashima, M.; Qiu, Y.; Spoors, P. G.; Bertounesque, E.; Salvatore, B. A. J. Org. Chem. 1998, 63, 7596. (b) Smith, A. B., III; Cho, Y. S.; Friestad, G. K. Tetrahedron Lett. 1998, 39, 8765. (c) Iwashima, M.; Kinsno, T.; Smith, A. B., III. Tetrahedron Lett. 1995, 36, 2199. (d) Smith, A. B., III; Iwashima, M. Tetrahedron Lett. 1994, 55, 6051. (e) Salvatore, B. A.; Smith, A. B., III. Tetrahedron Lett. 1994, 35, 1329. (f) Smith, A. B., III; Salvatore, B. A.; Hull, K. G.; Duan, J. J.-W. Tetrahedron Lett. 1991, 32, 4859. (g) Smith, A. B., III; Duan, J. J.-W.; Hull, K. G.; Salvatore, B. A. Tetrahedron Lett. 1991, 32, 4855.
7. Preliminary communications: (a) Smith, A. B., III; Friestad, G. K.; Duan, J. J.-W.; Barbosa, J.; Hull, K. G.; Iwashima, M.; Qiu, Y.; Spoors, P. G.; Bertounesque, E.; Salvatore, B. A. J. Org. Chem. 1998, 63, 7596. (b) Smith, A. B., III; Cho, Y. S.; Friestad, G. K. Tetrahedron Lett. 1998, 39, 8765. (c) Iwashima, M.; Kinsno, T.; Smith, A. B., III. Tetrahedron Lett. 1995, 36, 2199. (d) Smith, A. B., III; Iwashima, M. Tetrahedron Lett. 1994, 55, 6051. (e) Salvatore, B. A.; Smith, A. B., III. Tetrahedron Lett. 1994, 35, 1329. (f) Smith, A. B., III; Salvatore, B. A.; Hull, K. G.; Duan, J. J.-W. Tetrahedron Lett. 1991, 32, 4859. (g) Smith, A. B., III; Duan, J. J.-W.; Hull, K. G.; Salvatore, B. A. Tetrahedron Lett. 1991, 32, 4855.
8. Preliminary communications: (a) Smith, A. B., III; Friestad, G. K.; Duan, J. J.-W.; Barbosa, J.; Hull, K. G.; Iwashima, M.; Qiu, Y.; Spoors, P. G.; Bertounesque, E.; Salvatore, B. A. J. Org. Chem. 1998, 63, 7596. (b) Smith, A. B., III; Cho, Y. S.; Friestad, G. K. Tetrahedron Lett. 1998, 39, 8765. (c) Iwashima, M.; Kinsno, T.; Smith, A. B., III. Tetrahedron Lett. 1995, 36, 2199. (d) Smith, A. B., III; Iwashima, M. Tetrahedron Lett. 1994, 55, 6051. (e) Salvatore, B. A.; Smith, A. B., III. Tetrahedron Lett. 1994, 35, 1329. (f) Smith, A. B., III; Salvatore, B. A.; Hull, K. G.; Duan, J. J.-W. Tetrahedron Lett. 1991, 32, 4859. (g) Smith, A. B., III; Duan, J. J.-W.; Hull, K. G.; Salvatore, B. A. Tetrahedron Lett. 1991, 32, 4855.
9. Preliminary communications: (a) Smith, A. B., III; Friestad, G. K.; Duan, J. J.-W.; Barbosa, J.; Hull, K. G.; Iwashima, M.; Qiu, Y.; Spoors, P. G.; Bertounesque, E.; Salvatore, B. A. J. Org. Chem. 1998, 63, 7596. (b) Smith, A. B., III; Cho, Y. S.; Friestad, G. K. Tetrahedron Lett. 1998, 39, 8765. (c) Iwashima, M.; Kinsno, T.; Smith, A. B., III. Tetrahedron Lett. 1995, 36, 2199. (d) Smith, A. B., III; Iwashima, M. Tetrahedron Lett. 1994, 55, 6051. (e) Salvatore, B. A.; Smith, A. B., III. Tetrahedron Lett. 1994, 35, 1329. (f) Smith, A. B., III; Salvatore, B. A.; Hull, K. G.; Duan, J. J.-W. Tetrahedron Lett. 1991, 32, 4859. (g) Smith, A. B., III; Duan, J. J.-W.; Hull, K. G.; Salvatore, B. A. Tetrahedron Lett. 1991, 32, 4855.
10. Preliminary communications: (a) Smith, A. B., III; Friestad, G. K.; Duan, J. J.-W.; Barbosa, J.; Hull, K. G.; Iwashima, M.; Qiu, Y.; Spoors, P. G.; Bertounesque, E.; Salvatore, B. A. J. Org. Chem. 1998, 63, 7596. (b) Smith, A. B., III; Cho, Y. S.; Friestad, G. K. Tetrahedron Lett. 1998, 39, 8765. (c) Iwashima, M.; Kinsno, T.; Smith, A. B., III. Tetrahedron Lett. 1995, 36, 2199. (d) Smith, A. B., III; Iwashima, M. Tetrahedron Lett. 1994, 55, 6051. (e) Salvatore, B. A.; Smith, A. B., III. Tetrahedron Lett. 1994, 35, 1329. (f) Smith, A. B., III; Salvatore, B. A.; Hull, K. G.; Duan, J. J.-W. Tetrahedron Lett. 1991, 32, 4859. (g) Smith, A. B., III; Duan, J. J.-W.; Hull, K. G.; Salvatore, B. A. Tetrahedron Lett. 1991, 32, 4855.
11. Preliminary communications: (a) Smith, A. B., III; Friestad, G. K.; Duan, J. J.-W.; Barbosa, J.; Hull, K. G.; Iwashima, M.; Qiu, Y.; Spoors, P. G.; Bertounesque, E.; Salvatore, B. A. J. Org. Chem. 1998, 63, 7596. (b) Smith, A. B., III; Cho, Y. S.; Friestad, G. K. Tetrahedron Lett. 1998, 39, 8765. (c) Iwashima, M.; Kinsno, T.; Smith, A. B., III. Tetrahedron Lett. 1995, 36, 2199. (d) Smith, A. B., III; Iwashima, M. Tetrahedron Lett. 1994, 55, 6051. (e) Salvatore, B. A.; Smith, A. B., III. Tetrahedron Lett. 1994, 35, 1329. (f) Smith, A. B., III; Salvatore, B. A.; Hull, K. G.; Duan, J. J.-W. Tetrahedron Lett. 1991, 32, 4859. (g) Smith, A. B., III; Duan, J. J.-W.; Hull, K. G.; Salvatore, B. A. Tetrahedron Lett. 1991, 32, 4855.
12. Matsunaga, S.; Fujiki, H.; Sakata, D.; Fusetani, N. Tetrahedron 1991, 47, 2999.
13. Ogima, M.; Hyuga, S.; Hara, S.; Suzuki, A. Chem. Lett. 1989, 1959.
14. (b) For a review on Suzuki coupling, see: Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
15. Rand, C. L.; Van Horn, D. E.; Moore, M. W.; Negishi, E.-I. J. Org. Chem. 1981, 46, 4093. Zirconium-catalyzed carboalumination, followed by quenching with iodine and protection of the allylic hydroxyl as the t-butyldimethylsilyl ether furnished 6a,b from the corresponding propargylic alcohols.
16. Bhattacharya, A. K.; Thyagarajan, G. Chem. Rev. 1981, 81, 415.
17. The difficult methylation was consistent with reports by Evans et al. of the low reactivity of 13, prepared by a different method, which did not undergo normal Horner-Emmons coupling, see: Evans, D. A.; Gage, J. R.; Leighton, J. L. J. Am. Chem. Soc. 1992, 114, 9434.
18. Engel, R. Synthesis of Carbon-Phosphorous Bonds; CRC Press: Boca Raton, FL, 1988; p 7.
19. Uenishi, J.-I.; Beau, J.-M.; Armstrong, R. W.; Kishi, Y. J. Am. Chem. Soc. 1987, 109, 4756.
20. Unstable phosphonate A was best stored in a frozen benzene solution, from which anhydrous A could be obtained upon concentration in vacuo (with azeotropic removal of adventitious moisture). Under these conditions, storage of A for up to one month had no detrimental effect on subsequent Horner-Emmons reactions.
21. (a) Evans, D. A.; Bartroli, J.; Shih, T. L. J. Am. Chem. Soc. 1981, 103, 2127.
22. (b) Evans, D. A.; Ennis, M. D.; Mathre, D. J. J. Am. Chem. Soc. 1982, 104, 1737.
23. Tanner, D.; Somfai, P. Tetrahedron 1986, 42, 5985.
24. (b) Eliel, E. L.; Badding, V. G.; Rerick, M. N. J. Am. Chem. Soc. 1962, 84, 2371.
25. Davidson, D.; Weiss, M.; Jelling, M. J. Org. Chem. 1937, 2, 328.
26. The Davidson oxazole cyclization has been employed successfully in a variety of cases in which the product oxazoles are 2,4,5-trisubstituted; low yields are typical for 2,4-disubstituted or monosubstituted oxazoles. This is likely due to reduced regiocontrol in enamine formation (i.e., i vs ii) during the cyclization; the reaction is more successful when the substituent at C(5) is aromatic. See Theilig, G. Chem. Der. 1953, 86, 96. (Matrix Presented)
27. Evans, D. A.; Britton, T. C.; Ellman, J. A. Tetrahedron Lett. 1987, 28, 6141.
28. Yamada, S.; Kasai, Y.; Shioiri, T. Tetrahedron Lett. 1973, 14, 1595.
29. For example, see: (a) Hamada, Y.; Shibata, M.; Shioiri, T. Tetrahedron Lett. 1985, 26, 5155. (b) Hamada, Y.; Shibata, M.; Shioiri, T. Tetrahedron Lett. 1985, 26, 6501.
30. For example, see: (a) Hamada, Y.; Shibata, M.; Shioiri, T. Tetrahedron Lett. 1985, 26, 5155. (b) Hamada, Y.; Shibata, M.; Shioiri, T. Tetrahedron Lett. 1985, 26, 6501.
31. Evans, D. L.; Minster, D. K.; Jordis, U.; Hecht, S. M.; Mazzu, A. L., Jr.; Meyers, A. I. J. Org. Chem. 1979, 44, 497.
32. Yonetani, K.; Hirotsu, Y.; Shiba, T. Bull. Chem. Soc. Jpn. 1975, 48, 3302.
33. Anderson, R. C.; Shapiro, M. J. J. Org. Chem. 1984, 49, 1304.
34. Silks, L. A., III; Dunlap, R. B.; Odom, J. D. J. Am. Chem. Soc. 1990, 112, 4979.
35. (b) Silks, L. A., III; Peng, J.; Odom, J. D.; Dunlap, R. B. J. Org. Chem. 1991, 56, 6733.
36. Burgess E. M.; Penton, H. R., Jr.; Taylor, E. A.; Williams, W. M. Organic Syntheses; Wiley & Sons: New York, 1988; Collect. Vol. VI, p 788.
37. (b) Burgess, E. M.; Penton, H. R., Jr.; Taylor, E. A. J. Org. Chem. 1973, 38, 26.
38. Wipf, P.; Miller, C. P. Tetrahedron Lett. 1992, 33, 907.
39. Barrish, J. C.; Singh, J.; Spergel, S. H.; Han, W.-C.; Kissick, T. P.; Kronenthal, D. R.; Mueller, R. H. J. Org. Chem. 1993, 58, 4494.
40. Barrish-Singh oxidation did not compromise the integrity of the C(30) stereocenter, as judged by analysis of the optical rotation of (-)-D produced in this fashion.
41. Hamada, Y.; Kawai, A.; Kohno, Y.; Hara, O.; Shioiri, T. J. Am. Chem. Soc. 1989, 111, 1524.
42. (b) Hamada, Y.; Hara, O.; Kawai, A.; Kohno, Y.; Shioiri, T. Tetrahedron 1991, 47, 8635.
43. Sakura, N.; Ito, K.; Sekiya, M. Chem. Pharm. Bull. 1972, 20, 1156.
44. Yoshimura, J.; Yamaura, M.; Suzuki, T.; Hashimoto, H. Chem. Lett. 1983, 1001.
45. Heitz, M.-P.; Overman, L. E. J. Org. Chem. 1989, 54, 2591.
46. Lactone (-)-54 can be prepared from D-isoascorbic acid, see: Cohen, N.; Banner, B. L.; Laurenzano, A. J.; Carozza, L. Org. Synth. 1985, 63, 127.
47. Basha, A.; Lipton, M.; Weinreb, S. M. Tetrahedron Lett. 1977, 18, 4171.
48. Single-crystal X-ray analysis of 56 (major anomer) identified it as the β-anomer as expected on steric grounds.
49. Ludwig, C.; Wistrand, L.-G. Acta Chem. Scand. 1990, 44, 707.
50. (b) Skrinjar, M.; Wistrand, L.-G. Tetrahedron Lett. 1990, 31, 1775.
51. 3N; PhSH; monoperoxyphthalic acid magnesium salt hydrate (MMPP); 67% overall] were similarly unsuccessful. (Matrix Presented) For related examples, see: Brown, D. S.; Hansson, T.; Ley, S. V. Synlett 1990, 48. Brown, D. S.; Charreau, P.; Ley, S. V. Synlett 1990, 749.
52. 3N; PhSH; monoperoxyphthalic acid magnesium salt hydrate (MMPP); 67% overall] were similarly unsuccessful. (Matrix Presented) For related examples, see: Brown, D. S.; Hansson, T.; Ley, S. V. Synlett 1990, 48. Brown, D. S.; Charreau, P.; Ley, S. V. Synlett 1990, 749.
53. 1H NMR coupling constant analysis and confirmed by single-crystal X-ray analysis.
54. Shono, T.; Matsumura, Y.; Tsubata, K. J. Am. Chem. Soc. 1981, 103, 1172.
55. (b) Shono, T.; Tsubata, K.; Okinaga, N. J. Org. Chem. 1984, 49, 1056.
56. House, H. O.; Czuba, L. J.; Gall, M.; Olmstead, H. D. J. Org. Chem. 1969, 34, 2324.
57. Corey, E. J.; Nicolaou, K. C.; Balanson, R. D.; Machida, Y. Synthesis 1975, 590.
58. Flynn, D. L.; Zelle, R. E.; Grieco, P. A. J. Org. Chem. 1983, 48, 2424.
59. The acetonide required strongly acidic: conditions (CSA, MeOH, 45°C, 24 h or 1.2 M aqueous HCl, THF, 50°C, 12 h) to effect removal from model compound i, casting uncertainty upon its successful removal from fully protected calyculin. Indeed, although model compound iii could be deprotected, removal of the acetonide was unsuccessful with fully protected calyculin A. (b) Proton NMR comparison showed that cyclopentylidene hydrolysis from ii was 4.9 times faster than acetonide hydrolysis from i. (Matrix Presented)
60. (a) Toshima, K.; Mukaiyama, S.; Kinoshita, M.; Tatsuta, K. Tetrahedron Lett. 1989, 30, 6413.
61. (b) Spoors, P. G.; Smith, A. B., III, unpublished results.
62. Hamada, Y.; Kato, S.; Shioiri, T. Tetrahedron Lett. 1985, 26, 3223.
63. Zhao, Z.; Scarlato, G. R.; Armstrong, R. W. Tetrahedron Lett. 1991, 32, 1609.
64. The role of the phosphorous ligands on the stereoselectivity in Wittig reactions has been discussed in detail, see: Vedejs, E.; Marth, C. F. J. Am. Chem. Soc. 1988, 110, 3948.
65. Compounds 74 and 75 were prepared from i, the latter prepared during the synthesis of the C(9-25) fragment (+)-BC (see ref 1). O-Methylation, hydrogenation (Pearlman's catalyst) to saturate fully the alkyne, and removal of the C(25) O-benzyl afforded the C(25) primary alcohol. Ley oxidation (TPAP/NMO). with and without prior removal of the C(17) TBS group provided 74 and 75, respectively. (Matrix Presented)
66. Independently, Armstrong demonstrated similar transformations with the C(17) hydroxyl unprotected, see: Ogawa, A. K.; DeMattei, J. A.; Scarlato, G. R.; Tellew, J. E.; Chona, L. S.; Armstrong, R. W. J. Org. Chem. 1996, 61, 6153.
67. Ley, S. V.; Norman, J.; Griffith, W. P.; Marsden, S P. Synthesis 1994, 639.
68. 3, MeCN/THF; 28% yield).
69. This reductive deprotection initially provided variable yields and low mass balance. We speculate that chelation of the Lewis acidic boron and aluminum reagents by the C(36-37) permethylated 1,2-amino alcohol increased the product hydrophilicity and interfered with isolation; related C(9-25) substrates not possessing the 1,2-amino alcohol (i.e , before Wittig coupling) behaved normally.
70. If the C(36) tertiary amine is oxidized, the N-oxide product may be expected to be functionally similar to NMO. We did not detect the N-oxide.
71. 1H NMR spectroscopy was unreliable at this stage due to decomposition and the presence of interfering resonances
72. We benefited significantly in this regard from the previous successes of Evans (see ref 9) and Masamune (see: Tanimoto, N.; Gerritz, S. W.; Sawabe, A.; Noda, T.; Filla, S. A.; Masamune, S. Angew. Chem. Int. Ed. Engl. 1994, 33, 673), each of whom demonstrated that calyculin A is stable to HF in aqueous acetonitrile.
73. 9 In our case, the phosphate group is last to be deprotected. Deprotection at C(11) appears normal; this implicates the free phosphate as critical for the folding process. Similar behavior was observed during deprotections of calyculins A and B.
74. Synthetic (+)-calyculin A and (-)-calyculin B had optical rotations and CD spectra of equal magnitudes and opposite signs relative to the corresponding natural products.
75. We thank Professors Nobuhiro Fusetani and Shigeki Matsunaga (University of Tokyo) for authentic samples of natural (-)-1 and (+)-2, and for confirming that natural 2 has an [α] of +15° (c 0.07). Natural 2 was originally reported to have [α] -60° (c 0.05). We also thank Professor David Evans (Harvard University) for a sample of synthetic (+)-1.