A general approach to the basiliolide/transtaganolide natural products: Total syntheses of basiliolide B, epi-8-basiliolide B, transtaganolide C, and transtaganolide D

Angewandte Chemie - International Edition

Volumn 50, Issue 16, 2011, Pages 3688-3691

  Nelson, Hosea M ^a   Murakami, Kei ^a   Virgil, Scott C ^a   Stoltz, Brian M ^a  

^a CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

Acetylides; C C coupling reactions; Claisen rearrangement; Diels Alder reaction; Natural product synthesis

Indexed keywords

ACETYLIDES; C-C COUPLING REACTIONS; CLAISEN REARRANGEMENT; DIELS-ALDER REACTION; NATURAL PRODUCT SYNTHESIS;

ESTERS; ETHERS;

SYNTHESIS (CHEMICAL);

ARTEMISININ DERIVATIVE; BASILIOLIDE B; PYRONE DERIVATIVE; TRANSTAGANOLIDE C; TRANSTAGANOLIDE D;

ARTICLE; CHEMISTRY; CONFORMATION; STEREOISOMERISM; SYNTHESIS; X RAY CRYSTALLOGRAPHY;

ARTEMISININS; CRYSTALLOGRAPHY, X-RAY; MOLECULAR CONFORMATION; PYRONES; STEREOISOMERISM;

EID: 79953682814     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201008003     Document Type: Article

References (37)

1. J. J. Rubal, F. J. Moreno-Dorado, F. M. Guerra, Z. D. Jorge, A. Saouf, M. Akssira, F. Mellouki, R. Romero-Garrido, G. M. Massanet, Phytochemistry 2007, 68, 2480-2486.
2. A. Saouf, F. M. Guerra, J. J. Rubal, F. J. Moreno-Dorado, M. Akssira, F. Mellouki, M. Lopez, A. J. Pujadas, Z. D. Jorge, G. M. Massanet, Org. Lett. 2005, 7, 881-884.
3. C. Navarrete, R. Sancho, F. J. Caballero, F. Pollastro, B. L. Fiebich, O. Sterner, G. Appendino, E. Munoz, J. Pharmacol. Exp. Ther. 2006, 319, 422-430.
4. G. Appendino, S. Prosperini, C. Valdivia, M. Ballero, G. Colombano, R. A. Billington, A. A. Genazzani, O. Sterner, J. Nat. Prod. 2005, 68, 1213-1217.
5. M. Treiman, C. Caspersen, S. B. Christensen, Trends Pharmacol. Sci. 1998, 19, 131-135.
6. H. Mizoguchi, H. Oguri, K. Tsuge, H. Oikawa, Org. Lett. 2009, 11, 3016-3019.
7. H. Oguri, Y. Yamagishi, T. Hiruma, H. Oikawa, Org. Lett. 2009, 11, 601-604.
8. J. Li, B. Zhou, Molecules 2010, 15, 1378-1397.
9. Recent reports suggest a mode of action independent of ATPase inhibition, see: a) D. Cardi, A. Pozza, B. Arnou, E. Marchal, J. D. Clausen, J. P. Andersen, S. Krishna, J. V. Møller, M. le Maire, C. Jaxel, J. Biol. Chem. 2010, 285, 26406-26416;
10. b) S. G. Valderramos, D. Scanfeld, A.-C. Uhlemann, D. A. Fidock, S. Krishna, Antimicrob. Agents Chemother. 2010, 54, 3842-3852.
11. H. M. Nelson, B. M. Stoltz, Org. Lett. 2008, 10, 25-28.
12. a) M. V. Kozytska, G. B. Dudley, Tetrahedron Lett. 2008, 49, 2899-2901;
13. b) M. V. Kozytska, G. B. Dudley, Abstracts of Papers, 234th National Meeting of the American Chemical Society, Boston, Aug 19-23, 2007, American Chemical Society, Washington, 2007, ORGN 1012;
14. c) M. V. Kozytska, G. B. Dudley, Abstracts of Papers, 58th Southeast Regional Meeting of the American Chemical Society, Augusta, Nov 1-4, 2006, American Chemical Society, Washington, 2006, SRM06 011;
15. d) "I. Siletanylmethyllithium, an ambiphilic siletane II. Synthetic approach to basiliolide B.": M. V. Kozytska, PhD Thesis, Florida State University College of Arts and Sciences, 2008.
16. X. Zhou, W. Wu, X. Liu, C.-S. Lee, Org. Lett. 2008, 10, 5525-5528.
17. H. M. Nelson, B. M. Stoltz, Tetrahedron Lett. 2009, 50, 1699-1701.
18. R. Larsson, O. Sterner, M. Johansson, Org. Lett. 2009, 11, 657-660.
19. At the time of submission, the authors have not been able to find any additional examples of such ring systems within naturally occurring compounds.
20. Although simple cross-couplings of halide 6 (X=Br or I, R= Me, R′=Me) with reagents such as vinyl tributylstannane were possible, neither Sonogashira-type reactions with alkoxyacetylenes nor other cross-coupling reactions with methoxyacetylide reagents were successful.
21. a) J. A. Marshall in Organometallics in Synthesis: A Manual (Ed.: M. Schlosser) Wiley, Chichester, 2002, pp.457;
22. b)T. Sakamoto, A. Yasuhara, Y. Kondo, H. Yamanaka, Synlett 1992, 502;
23. c) T. Sakamoto, A. Yasuhara, Y. Kondo, Y. Yamagishi, Chem. Pharm. Bull. 1994, 42, 2032-2035;
24. d) A. Löffler, G. Himbert, Synthesis 1992, 495-498.
25. Unpublished studies utilizing derivatives of commercially available ethoxyacetylene confirmed the effectiveness of analogous Stille couplings, while Negishi or Sonogashira-type couplings were non-productive in our hands.
26. For an analogous preparation of the lithioethoxyacetylide, see: S. Raucher, B. L. Bray, J. Org. Chem. 1987, 52, 2332-2333.
27. The hazards associated with the preparation of methoxyacetylene is well documented, see: a) E. R. H. Jones, G. Eglington, M. C.Whiting, B. L. Shaw, Org. Synth. 1954, 34, 46-49;
28. b) H.H. Wasserman, P. S.Wharton, J. Am. Chem. Soc. 1960, 82, 661-665;
29. c) J. R. Dombroski, C. Schuerch, Macromolecules 1970, 3, 257-260.
30. Silyl ester 6a could be prepared directly from ester 6a (X=I) under slightly modified reaction conditions, that is, using N,Obis(tert- butyldimethylsilyl)acetimide. However, the yield over three steps was significantly lower; ca. 10%.
31. E. J. Corey, A. Venkateswarlu, J. Am. Chem. Soc. 1972, 94, 6190-6191.
32. C. Dai, G. C. Fu, J. Am. Chem. Soc. 2001, 123, 2719-2724.
33. 4] to a solution of stannane 10 in DMF leads to comsumption of 10 and the formation of oligomeric products.
34. CCDC 796908 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data-request/cif.
35. H. Shibuya, K. Ohashi, N. Narita, T. Ishida, I. Kitagawa, Chem. Pharm. Bull. 1994, 42, 293-299.
36. 2 in a sealed vial at 165°C for 48 h also smoothly produces the Diels-Alder product.
37. Synthetic basiliolide B was spectroscopically indistinguishable from the natural product isolated from Thapsia sp., see ref. [4].