The total syntheses of basiliolide C, epi-basiliolide C, and protecting-group-free total syntheses of transtaganolides C and D

Journal of Organic Chemistry

Volumn 79, Issue 20, 2014, Pages 9740-9747

  Gordon, Jonny R ^a   Nelson, Hosea M ^a   Virgil, Scott C ^a   Stoltz, Brian M ^a  

^a California Institute of Technology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL EQUATIONS; CROSS-COUPLINGS; PALLADIUM-CATALYZED; PROTECTING-GROUP-FREE SYNTHESIS; QUATERNARY CENTERS; TERTIARY STEREOCENTERS; TOTAL SYNTHESIS; ZINC REAGENTS;

SYNTHESIS (CHEMICAL);

BASILIOLIDE C; EPI BASILIOLIDE C; METHOXY ALKYNYL ZINC; PALLADIUM; PLANT EXTRACT; REAGENT; TRANSTAGANOLIDE C; TRANSTAGANOLIDE D; UNCLASSIFIED DRUG; ARTEMISININ DERIVATIVE; DYES, REAGENTS, INDICATORS, MARKERS AND BUFFERS; PYRONE DERIVATIVE; ZINC;

ARTICLE; CHEMICAL REACTION; CROSS COUPLING REACTION; DIELS ALDER REACTION; DRUG STRUCTURE; DRUG SYNTHESIS; IRELAND CLAISEN REACTION; ONE POT SYNTHESIS; CHEMICAL STRUCTURE; CHEMISTRY; CYCLOADDITION; STEREOISOMERISM; SYNTHESIS;

ARTEMISININS; CYCLOADDITION REACTION; INDICATORS AND REAGENTS; MOLECULAR STRUCTURE; PALLADIUM; PYRONES; STEREOISOMERISM; ZINC;

EID: 84907978503     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo501924u     Document Type: Article

References (32)

1. (a) Christensen, S. B.; Rasmussen, U. Tetrahedron Lett. 1980, 21, 3829-3830.
2. (b) Christensen, S. B.; Andersen, A.; Smitt, U. W. Prog. Chem. Org. Nat. Prod. 1997, 71, 130-167.
3. Christensen, S. B.; Larsen, I. K.; Rasmussen, U.; Christophersen, C. J. Org. Chem. 1982, 47, 649-652.
4. Perchellet, E. M.; Gali, H. U.; Gao, X. M.; Perchellet, J. Int. J. Cancer 2006, 55, 1036-1043.
5. Lytton, J.; Westlin, M.; Hanley, M. R. J. Biol. Chem. 1991, 266, 17067-17071.
6. Treiman, T.; Caspersen, C.; Christensen, S. B. Trends Pharmacol. Sci. 1998, 19, 131-135.
7. (a) Saouf, A.; Guerra, F. M.; Rubal, J. J.; Moereno-Dorado, F. J.; Akssira, M.; Mellouki, F.; López, M.; Pujadas, A. J.; Jorge, Z. D.; Massanet, G. M. Org. Lett. 2005, 7, 881-884.
8. (b) Appendino, G.; Prosperini, S.; Valdivia, C.; Ballero, M.; Colombano, G.; Billington, R. A.; Genazzani, A. A.; Sterner, O. J. Nat. Prod. 2005, 68, 1213-1217.
9. Navarrete, C.; Sancho, R.; Caballero, F. J.; Pollastro, F.; Fiebich, B. L.; Sterner, O.; Appendino, G.; Muñoz, E. J. Pharmacol. Exp. Ther. 2006, 319, 422-430.
10. Through close correspondence with Appendino6b and Muñoz,7 it had come to our attention that even though the assayed transtaganolide and basiliolides (4, 6, and 8) were by all observable methods pure, trace thapsigargin (1) contamination was still a looming possibility. As a control, synthetically derived racemic transtaganolide C (4) was sent for biological testing and results were consistent with those observed from the isolated natural products, removing any possibility that the previously observed activity had resulted from trace thapsigargin (1) contamination.
11. (a) Kozytska, M. V.; Dudley, G. B. Tetrahedron Lett. 2008, 49, 2899-2901.
12. (b) Zhou, X.; Wu, W.; Liu, X.; Lee, C.-S. Org. Lett. 2008, 10, 5525-5528.
13. (c) Larsson, R.; Sterner, O.; Johansson, M. Org. Lett. 2009, 11, 657-660.
14. (a) Nelson, H. M.; Stoltz, B. M. Org. Lett. 2008, 10, 25-28.
15. (b) Nelson, H. M.; Stoltz, B. M. Tetrahedron Lett. 2009, 50, 1699-1701.
16. Nelson, H. M.; Murakami, K.; Virgil, S. C.; Stoltz, B. M. Angew. Chem., Int. Ed. 2011, 50, 3688-3691.
17. Nelson, H. M.; Gordon, J. R.; Virgil, S. C.; Stoltz, B. M. Angew. Chem., Int. Ed. 2013, 52, 6699-6703.
18. To enable convenient discussion of the previously unnamed natural metabolite 10, the authors have given the name "basiliopyrone" to metabolite 10 as it is believed to be a biosynthetically related to the basiliolide and transtaganolide (2-6 and 8) family of natural products.14
19. Rubal, J. J.; Moreno-Dorado, F. J.; Guerra, F. M.; Jorge, Z. D.; Saouf, A.; Akssira, M.; Mellouki, F.; Romero-Garrido, R.; Massanet, G. M. Phytochemistry 2007, 68, 2480-2486.
20. Larsson, R.; Scheeren, H. W.; Aben, R. W. M.; Johansson, M.; Sterner, O. Eur. J. Org. Chem. 2013, 6955-6960.
21. (a) Gordon, J.; Hamilton, C.; Hooper, A. M.; Ibbotson, H. C.; Kurosawa, S.; Mori, K.; Muto, S.; Pickett, J. A. Chem. Commun. 1999, 2335-2336.
22. (b) Imamura, Y.; Takikawa, H.; Mori, K. Tetrahedron Lett. 2002, 43, 5743-5746.
23. (a) Marshall, J. A. In Organometallics in Synthesis: A Manual; Schlosser, M., Ed.; Wiley: Chichester, U.K., 2002, 457.
24. (b) Sakamoto, T.; Yasuhara, A.; Kondo, Y.; Yamanaka, H. Synlett 1992, 502.
25. (c) Sakamoto, T.; Yasuhara, A.; Kondo, Y.; Yamanaka, H. Chem. Pharm. Bull. 1994, 42, 2032-2035.
26. Löffler, A.; Himbert, G. Synthesis 1992, 495-498.
27. Raucher, S.; Bray, B. L. J. Org. Chem. 1987, 52, 2332-2333.
28. Because of the instability of the methoxyethynyl zinc chloride (27), the organozinc reagent could not characterized, and the solution was used assuming a 100% theoretical yield of formation.
29. Kropp, P. J.; McNeely, S. A.; Davis, R. D. J. Am. Chem. Soc. 1983, 105, 6907-6915.
30. Van Leeuwen, P. W. N. M.; Kamer, P. C. J.; Reek, J. N. H.; Dierkes, P. Chem. Rev. 2000, 100, 2741-2769.
31. Van Leeuwen, P. W. N. M.; Zuideveld, M. A.; Swennenhuis, B. H. G.; Freixa, Z.; Kamer, P. C. J.; Goubitz, K.; Fraanje, J.; Lutz, M.; Spek, A. L. J. Am. Chem. Soc. 2003, 125, 5523-5539.
32. Kapferer, T.; Brückner, R. Eur. J. Org. Chem. 2006, 2119-2133.