Total synthesis of (-)-heptemerone B and (-)-guanacastepene E

Journal of the American Chemical Society

Volumn 128, Issue 51, 2006, Pages 17057-17062

  Miller, Aubry K ^a   Hughes, Chambers C ^a,b   Kennedy Smith, Joshua J ^a,c   Gradl, Stefan N ^a,d   Trauner, Dirk ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b UNIVERSITY OF CALIFORNIA   (United States)

^c ROCHE BIOSCIENCE   (United States)

^d SGX Pharmaceuticals Inc   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CUPRATE CONJUGATE ADDITIONS; ENANTIOMERS; INTRAMOLECULAR HECK REACTIONS; QUATERNARY STEREOCENTERS;

OXIDATION; PARAFFINS; REACTION KINETICS; SAPONIFICATION; STEREOCHEMISTRY; SYNTHESIS (CHEMICAL);

OLEFINS;

DITERPENOID; GUANACASTEPENE E; HEPTEMERONE B; NEODOLASTANE; UNCLASSIFIED DRUG;

ARTICLE; ASYMMETRIC CATALYSIS; ELECTROCHEMICAL ANALYSIS; ENANTIOMER; HECK REACTION; OXIDATION; REACTION ANALYSIS; REDUCTION KINETICS; RING CLOSING METATHESIS; SAPONIFICATION; STEREOCHEMISTRY; STRUCTURE ANALYSIS; SYNTHESIS;

CYCLIZATION; DITERPENES; MODELS, MOLECULAR; MOLECULAR STRUCTURE; OXIDATION-REDUCTION; STEREOISOMERISM;

EID: 33845935517     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0660507     Document Type: Article

References (84)

1. Guanacastepene isolation articles: (a) Brady, S. F.; Singh, M. P.; Janso, J. E.; Clardy, J. J. Am. Chem. Soc. 2000, 122, 2116-2117.
2. (b) Brady, S. F.; Bondi, S. M.; Clardy, J. J. Am. Chem. Soc. 2001, 123, 9900-9901.
3. Heptemerone isolation articles: (a) Valdivia, C.; Kettering, M.; Anke, H.; Thines, E.; Sterner, O. Tetrahedron 2005, 61, 9527-9532.
4. (b) Kettering, M; Valdivia, C.; Sterner, O.; Anke, H.; Thines, E. J. Antibiot. 2005, 58, 390-396.
5. For reviews on the total synthesis of guanacastepenes and related diterpenes, see: (a) Hiersemann, M. Nachr. Chem. 2006, 54, 29-33.
6. (b) Hiersemann, M.; Helmboldt, H. Top. Curr. Chem. 2005, 243, 73-136.
7. (c) Maifeld, S. V.; Lee, D. Synlett 2006, 1623-1644.
8. (d) Mischne, M. Curr. Org. Synth. 2005, 2, 261-279.
9. Singh, M. P.; Janso, J. E.; Luckman, S. W.; Brady, S. F.; Clardy, J.; Greenstein, M.; Maiese, W. M. J. Antibiot. 2000, 53, 256-261.
10. (a) Dudley, G. B.; Danishefsky, S. J. Org. Lett. 2001, 3, 2399-2402.
11. (b) Dudley, G. B.; Tan, D. S.; Kim, G.; Tanski, J. M.; Danishefsky, S. J. Tetrahedron Lett. 2001, 42, 6789-6791.
12. (c) Dudley, G. B.; Danishefsky, S. J.; Sukenick, G. Tetrahedron Lett. 2002, 43, 5605-5606.
13. (d) Tan, D. S.; Dudley, G. B.; Danishefsky, S. J. Angew. Chem., Im. Ed. 2002, 41, 2185-2188.
14. (e) Lin, S. N.; Dudley, G. B.; Tan, D. S.; Danishefsky, S. J. Angew. Chem., Int. Ed. 2002, 41, 2188-2191.
15. (f) Mandal, M.; Danishefsky, S. J. Tetrahedron Lett. 2004, 45, 3827-3829.
16. (g) Mandal, M.; Danishefsky, S. J. Tetrahedron Lett. 2004, 45, 3831-3833.
17. (h) Yun, H. D.; Meng, Z. Y.; Danishefsky, S. J. Heterocycles 2005, 66, 711-725.
18. (i) Yun, H. D.; Danishefsky, S. J. Tetrahedron Lett. 2005, 46, 3879-3882.
19. (j) Mandal, M.; Yun, H. D.; Dudley, G. B.; Lin, S. N.; Tan, D. S.; Danishefsky, S. J. J. Org. Chem. 2005, 70, 10619-10637.
20. (k) Cheong, P. H. Y.; Yun, H.; Danishefsky, S. J.; Houk, K. N. Org. Lett. 2006, 8, 1513-1516.
21. (l) Snider, B. B.; Hawryluk, N. A. Org. Lett. 2001, 3, 569-572.
22. (m) Snider, B. B.; Shi, B. Tetrahedron Lett. 2001, 42, 9123-9126.
23. (n) Shi, B.; Hawryluk, N. A.; Snider, B. B. J. Org. Chem. 2003, 68, 1030-1042.
24. (o) Boyer, F. D.; Hanna, I. Tetrahedron Lett. 2002, 43, 7469-7472.
25. (p) Boyer, F. D.; Hanna, I.; Ricard, L. Org. Lett. 2004, 6, 1817-1820.
26. (q) Boyer, F. D.; Hanna, I. J. Org. Chem. 2005, 70, 1077-1080.
27. (r) Mehta, G.; Umarye, J. D. Org. Lett. 2002, 4, 1063-1066.
28. (s) Mehta, G.; Umarye, J. D.; Gagliardini, V. Tetrahedron Lett. 2002, 43, 6975-6978.
29. (t) Mehta, G.; Umarye, J. D.; Srinivas, K. Tetrahedron Lett. 2003, 44, 4233-4237.
30. (u) Mehta, G.; Umarye, J. D. Tetrahedron Lett. 2003, 44, 7285-7289.
31. (v) Mehta, G.; Pallavi, K.; Umarye, J. D. Chem. Commun. 2005, 4456-4458.
32. (w) Shipe, W. D.; Sorensen, E. J. Org. Lett. 2002, 4, 2063-2066.
33. (x) Shipe, W. D.; Sorensen, E. J. J. Am. Chem. Soc. 2006, 128, 7025-7035.
34. (y) limura, S.; Overman, L. E.; Paulini, R.; Zakarian, A. J Am. Chem. Soc. 2006, 128, 13095-13101.
35. (z) Magnus, P.; Waring, M. J.; Ollivier, C.; Lynch, V. Tetrahedron Lett 2001, 42, 4947-4950.
36. (aa) Magnus, P.; Ollivier, C. Tetrahedron Lett. 2002, 43, 9605-9609.
37. (ab) Nguyen, T. M.; Lee, D. Tetrahedron Lett. 2002, 43, 4033-4036.
38. (ac) Nguyen, T. M.; Seifert, R. J.; Mowrey, D. R.; Lee, D. S. Org. Lett. 2002, 4, 3959-3962.
39. (ad) Nakazaki. A.; Sharma, U.; Tius, M. A. Org. Lett. 2002, 4, 3363-3366.
40. (ae) Du, X. H.; Chu, H. F. V.; Kwon, O. Org. Lett. 2003, 5, 1923-1926.
41. (af) Du, X. H.; Chu, H. F. V.; Kwon, O. Y. Tetrahedron Lett. 2004, 45, 8843-8846.
42. (ag) Srikrishna, A.; Dethe, D. H. Org. Lett. 2004, 6, 165-168.
43. (ah) Chiu, P.; Li, S. L. Org. Lett. 2004, 6, 613-616.
44. (ai) Brummond, K. M.; Gao, D. Org. Lett. 2003, 5, 3491-3494.
45. (aj) Sarpong, R.; Su, J. T.; Stoltz, B. M. J. Am. Chem. Soc. 2003, 125, 13624-13625.
46. (ak) Li, C. C.; Liang, S.; Zhang, X. H.; Xie, Z. X.; Chen, J. H.; Wu, Y. D.; Yang, Z. Org. Lett. 2005. 7, 3709-3712.
47. (al) Li, C. C.; Wang, C. H.; Liang, B.; Zhang, X. H.; Deng, L. J.; Liang, S.; Chen. J. H.; Wu, Y. D.; Yang, Z. J. Org. Chem. 2006, 71, 6892-6897.
48. (am) Gradl, S. N.; Kennedy-Smith, J. J.; Kim, J.; Trauner, D. Synlett 2002, 411-414.
49. (an) Hughes, C. C.; Kennedy-Smith, J. J.; Trauner, D. Org. Lett. 2003, 5, 4113-4115.
50. (ao) Hughes, C. C.; Miller, A. K.; Trauner, D. Org. Lett. 2005, 7, 3425-3428.
51. Kraus, G. A.; Wang, X. Synth. Commun. 1998, 28, 1093-1096.
52. (a) Rege, P. D.; Malkina.O. L.; Goroff. N. S. J. Am. Chem. Soc. 2002, 124, 370-371.
53. (b) Webb, J. A.; Klijn, J. E.; Hill, P. A.; Bennett, J. L.; Goroff, N. S. J. Org. Chem. 2004, 69, 660-664.
54. For a review of asymmetric intramolecular Heck reactions, see: (a) Donde, Y.; Overman, L. E. In Catalytic Asymmetric Synthesis, 2nd ed.; Ojima, I., Ed.; Wiley: New York, 2000; pp 675-697.
55. Jeffery, T. Tetrahedron 1996, 52, 10113-10130.
56. Brown, H. C.; Chandrasekharan, J.; Ramachandran, P. V. J. Am. Chem. Soc. 1988, 110, 1539-1546.
57. Appel, R. Angew. Chem., Int. Ed. 1975, 14, 801-811.
58. (a) Whitesell, J. K.; Chen, H.-H.; Lawrence, R. M. J. Org. Chem. 1985, 50, 4663-4664.
59. (b) Whitesell, J. K.; Lawrence, R. M.; Chem, H.-H. J. Org. Chem. 1985, 50, 4779-4784.
60. For a review on cyclohexyl-based chiral auxiliaries, see: (c) Whitesell, J. K. Chem. Rev. 1992, 92, 953-964.
61. Racemic trans-2-phenylcyclohexanol was made according to: (d) Schwartz, A.; Madan, P.; Whitesell, J. K.; Lawrence, R. M. Org. Synth. Coll. Vol. 8 1993, 516.
62. A recently reported enzymatic resolution of racemic trans-2- phenylcyclohexanol was found to be extremely efficient and easy to run on large scale: She, Y.-H.; Wu, C-F.; Shia, K.-S.; Wu, J.-D.; Peddinti, R. K.; Liu. H.-J. Synthesis 2005, 749-752.
63. In the racemic series, the two diastereomers could be separated by fractional crystallization, and the relative stereochemistry of the major product was secured with the X-ray structure of (±)-26 (see Supporting Information). Enantiomerically pure 26, by contrast, was not a solid, and the two diastereomers proved to be inseparable by Chromatographic methods. Therefore, we proceeded with the 10:1 mixture of diastereomers until formation of 29, wherein the two diastereomers could be easily separated by silica gel chromatography.
64. Takeda, N.; Imamoto, T. Org. Synth. Coll. Vol. 10 2004, p 200.
65. For a related RCM reaction on a model system, see ref 5am. The ring-closing metathesis reaction of enone 28 to cyclopentenone 29 has also been reported in a thesis from the MacMillan group: Jen, W. S. Development of New Asymmetric Organocatalytic Methods and Progress Towards the Total Synthesis of Guanacastepene A. California Institute of Technology, Pasadena, CA, 2003 (available at http://etd.caltech.edu/etd/available/etd- 10282003-1358.7/, accessed November, 2006).
66. (a) Lipshutz, B. H.; Koerner, M.; Parker, D. A. Tetrahedron Lett. 1987, 28, 945-948.
67. (b) Lipshutz, B. H. Synthesis 1987, 325-341.
68. (c) Ibuka, T.; Yamamoto, Y. In Organocopper Reagents: A Practical Approach; Taylor, R. J. K., Ed.; Oxford: Oxford, U.K., 1994; Chapter 7, p 143.
69. See ref 5ao for a model study of this conjugate addition. A similar linkage was explored in Overman et al.'s synthesis of guanacastepene N (ref 5y).
70. Cyclopentanone 31 was isolated along with significant amounts of the corresponding 1,2 adduct (see Supporting Information).
71. Baran and co-workers have recently reported the chemical oxidative coupling of enolates with indoles and pyrroles: (a) Richter, J. M.; Baran, P. S. J. Am. Chem. Soc. 2004, 126, 7450-7451.
72. (b) Baran, P. S.; Richter, J. M.; Lin, D. W. Angew. Chem., Int. Ed. 2005, 44, 609-612.
73. (c) Richter, J. M.; Baran, P. S. J. Am. Chem. Soc. 2005, 127, 15394-15396.
74. (a) Mihelcic, J.; Moeller, K. D. J. Am. Chem. Soc. 2004, 126, 9106-9111.
75. (b) Mihelcic, J.; Moeller, K. D. J. Am. Chem. Sac. 2003, 125, 36-37.
76. (c) Wright, D. L.; Whitehead, C. R.; Sessions, E. H.; Ghiviriga, I.; Frey, D. A. Org. Lett. 1999, 1, 1535-1538.
77. (d) Whitehead, C. R.; Sessions, E. H.; Ghiviriga, I.; Wright, D. L. Org. Lett. 2002, 4, 3763-3765.
78. (e) Sperry, J. B.; Whitehead, C. R.; Ghiviriga, I.; Walczak, R. M.; Wright, D. L. J. Org. Chem. 2004, 69, 3726-3734.
79. (f) Sperry, J. B.; Wright, D. L. J. Am. Chem. Soc. 2005, 127, 8034-8035.
80. (g) Sperry, J. B.; Wright, D. L. Tetrahedron 2006, 62, 6551-6557.
81. (h) Sperry, J. B.; Ghiviriga, I. Wright, D. L. Chem. Commun. 2006, 2, 194-196.
82. For reviews of anodic electrochemistry, see (i) Moeller, K. D. Tetrahedron 2000, 56, 9527-9554.
83. and (j) Sperry, J. B.; Wright, D. L. Chem. Sov. Rev. 2006, 35, 605-621.
84. The optical rotation of natural guanacastepene E was not reported in the original isolation study (ref Ib). The literature value reported here is from synthetic guanacastepene E (ref 6x).