Polycyclic molecules from linear precursors: Stereoselective synthesis of clavolonine and related complex structures

Angewandte Chemie - International Edition

Volumn 44, Issue 37, 2005, Pages 6038-6042

  Evans, David A ^a   Scheerer, Jonathan R ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

Alkaloids; Michael addition; Natural products; Polycycles; Synthetic methods

Indexed keywords

ADDITION REACTIONS; CARBON; COMPLEXATION; STEREOCHEMISTRY; SYNTHESIS (CHEMICAL);

ALKALOIDS; MICHAEL ADDITION; NATURAL PRODUCTS; POLYCYCLES; SYNTHETIC METHODS;

POLYCYCLIC AROMATIC HYDROCARBONS;

CLAVOLONINE; QUINOLIZINE DERIVATIVE;

ARTICLE; CHEMICAL STRUCTURE; CYCLIZATION; STEREOISOMERISM; SYNTHESIS; X RAY CRYSTALLOGRAPHY;

CRYSTALLOGRAPHY, X-RAY; CYCLIZATION; MOLECULAR STRUCTURE; QUINOLIZINES; STEREOISOMERISM;

EID: 25144504941     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200502296     Document Type: Article

References (42)

1. a) D. B. McLean, The Alkaloids: Chemistry and Physiology, Vol. 14 (Ed.: R. H. F. Manske), Academic Press, New York, 1973, p. 347;
2. b) D. B. McLean, The Alkaloids: Chemistry and Physiology, Vol. 10 (Ed.: R. H. F. Manske), Academic Press, New York, 1968, p. 305;
3. c) J. C. Braekman, L. Nyembo, P. Bourdoux, N. Kahindo, C. Hootele, Phytochemistry 1974, 13, 2519;
4. d) W. A. Ayer, G. C. Kasitu, Can. J. Chem. 1989, 67, 1077;
5. e) M. Castillo, L. A. Loyola, G. Morales, I. Singh, C. Calvo, H. L. Holland, D. B. MacLean, Can. J. Chem. 1976, 54, 2893.
6. a) C. H. Heathcock, E. F. Kleinman, E. S. Binkley, J. Am. Chem. Soc. 1982, 104, 1054;
7. b) G. Stork, R. A. Kretchmer, R. H. Schlessinger, J. Am. Chem. Soc. 1968, 90, 1647;
8. c) W. A. Ayer, W. R. Bowman, T. C. Joseph, P. Smith, J. Am. Chem. Soc. 1968, 90, 1648;
9. d) G. A. Kraus, Y. S. Hon, J. Am. Chem. Soc. 1985, 107, 4341;
10. e) A. Padwa, M. A. Brodney, J. P. Marino, S. M. Sheehan, J. Org. Chem. 1997, 62, 78;
11. f) P. A. Grieco, Y. J. Dai, J. Am. Chem. Soc. 1998, 120, 5128;
12. g) M. Mori, K. Hori, M. Akashi, M. Hori, Y. Sato, M. Nishida, Angew. Chem. 1998, 110, 659;
13. Angew. Chem. Int. Ed. 1998, 37, 636. For reviews of lycopodium alkaloid chemistry, see also references [1a,b].
14. a) R. H. Burnell, D. R. Taylor, Chem. Ind. 1960, 1239;
15. b) R. H. Burnell, B. S. Mootoo, Can. J. Chem. 1961, 39, 1090.
16. a) E. Wenkert, C. A. Broka, J. Chem. Soc. Chem. Commun. 1984, 714;
17. b) E. Wenkert, B. Chauncy, K. G. Dave, A. R. Jeffcoat, F. M. Schell, H. P. Schenk, J. Am. Chem. Soc. 1973, 95, 8427.
18. W. C. Still, I. Galynker, Tetrahedron 1981, 37, 3981.
19. D. A. Evans, S. L. Bender, J. Morris, J. Am. Chem. Soc. 1988, 110, 2506.
20. Abbreviations: 9-BBN = 9-borabicyclo[3.3.1]nonane; Bn = benzyl; Boc = tert-butyloxycarbonyl; DibalH = diisobutylaluminum hydride; DMAP = 4-dimethylaminopyridine; DMP = Dess-Martin periodinane; DMF = N,N-dimethylformamide; DMS = dimethyl sulfide; DMSO = dimethyl sulfoxide; imid = imidazole; LDA = lithium diisopropylamide; PPTS = pyridinium p-toluenesulfonate; py = pyridine; TBDPS = tert-butyldiphenylsilyl; TBSCl = tert-butyldimethylsilyl chloride; TESCl = triethylsilyl chloride; TFA = trifluoroacetic acid; TMSOTf = trimethylsilyl trifluoromethanesulfonate; TsOH = p-toluenesulfonic acid.
21. β-Ketophosphonate 7 was prepared in four steps from the previously synthesized protected δ-amino valeric acid 6: D. L. Flynn, R. E. Zelle, P. A. Grieco, J. Org. Chem. 1983, 48, 2425.
22. C. R. Holmquist, E. J. Roskamp, J. Org. Chem. 1989, 54, 3258.
23. a) P. Deslongchamps, Pure Appl. Chem. 1996, 68, 1831;
24. b) D. A. Evans, J. T. Starr, Angew. Chem. 2002, 114, 1865;
25. Angew. Chem. Int. Ed. 2002, 41, 1787;
26. c) D. A. Evans, J. T. Starr, J. Am. Chem. Soc. 2003, 125, 13 531.
27. 1H NMR or IR spectroscopy. For this reason, the ketone at C13 should be regarded as a saturated ketone.
28. Macrocycle 11a was decarboxylated under Krapcho conditions. This material also exclusively favors condensation at C5.
29. 1H NMR spectral analysis (NOESY).
30. a) G. Stork, J. D. Winkler, N. A. Saccomano, Tetrahedron Lett. 1983, 24, 465;
31. b) G. Stork, C. S. Shiner, J. D. Winkler, J. Am. Chem. Soc. 1982, 104, 310;
32. c) E. M. Arnett, S. G. Maroldo, S. L. Schilling, J. A. Harrelson, J. Am. Chem. Soc. 1984, 106, 6759;
33. d) M. Raban, D. P. Haritos, J. Am. Chem. Soc. 1979, 101, 5178;
34. e) M. Raban, E. A. Noe, G. Yamamoto, J. Am. Chem. Soc. 1977, 99, 6527;
35. f) L. M. Jackman, B. C. Lange, Tetrahedron 1977, 33, 2737.
36. L. N. Mander, S. G. Pyne, J. Am. Chem. Soc. 1979, 101, 3373.
37. Product 30d was prepared independently by alkylation of 28 with 1-iodo-3-amino-tert-butylcarbamate and tBuOK provided 30d as a single isomer in less than 30% yield.
38. The use of methanolic HCl to effect a Mannich addition finds precedent in the Heathcock synthesis of lycopodine; see reference [2a].
39. C. H. Heathcock, M. H. Norman, D. A. Dickman, J. Org. Chem. 1990, 55, 798.
40. a) R. V. Stevens, A. W. M. Lee, J. Am. Chem. Soc. 1979, 101, 7032;
41. b) R. V. Stevens, Acc. Chem. Res. 1984, 17, 289.
42. 2: a = 13.5174(12), c = 7.7656(10), space group P41.