Total synthesis of eudesmane terpenes by site-selective C-H oxidations

Nature

Volumn 459, Issue 7248, 2009, Pages 824-828

  Chen, Ke ^a   Baran, Phil S ^a  

^a SCRIPPS RESEARCH INSTITUTE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; CARBON; EUDESMANE DERIVATIVE; HYDROGEN; POLYENE; TERPENE DERIVATIVE;

ALKENE; CHEMICAL BONDING; ENZYME ACTIVITY; MOLECULAR ANALYSIS; OXIDATION; TERPENE;

ARTICLE; BIOSYNTHESIS; CYCLIZATION; ENANTIOSELECTIVITY; ENZYME ACTIVITY; HYDROGEN BOND; ORGANIC CHEMISTRY; OXIDATION; PRIORITY JOURNAL; REACTION ANALYSIS; STEREOCHEMISTRY;

BIOLOGICAL PRODUCTS; BIOMIMETICS; CARBON; HYDROGEN; MOLECULAR STRUCTURE; OXIDATION-REDUCTION; SESQUITERPENES; SESQUITERPENES, EUDESMANE;

EID: 67349149964     PISSN: 00280836     EISSN: 14764687     Source Type: Journal    
DOI: 10.1038/nature08043     Document Type: Article

References (30)

1. Nicoiaou, K. C. & Montagnon, T. Molecules That Changed the World (Wiley-VCH, 2008).
2. Davis, E. M. & Croteau, R. Cyclizaton enzymes in the biosynthesis of monoterpenes, sesquiterpenes and dlterpenes, Top. Curr. Chem. 209, 53-95 (2000).
3. Maimone, T. J. & Baran, P. S. Modern synthetic efforts toward biologically active terpenes, Nature Chem. Biol. 3, 396-407 (2007). (Pubitemid 46956320)
4. Corey, E. J. & Cheng, X. M. The Logic of Chemical Synthesis (Wiley, 1995).
5. Wilson, R. & Danishefsky, S. J. Pattern recognition in retrosynthetic analysis: snapshots in total synthesis, J. Org. Chem. 72, 4293-4305 (2007). (Pubitemid 46903297)
6. Yoder, R. A. & Johnston, J. N. A case study in biomimetic total synthesis: poiyoiefin carbocyclizations to terpenes and steroids, Chem. Rev. 105, 4730-4756 (2005). (Pubitemid 43092002)
7. Ruzlcka, L. lsoprene rule and the biogenesis of terpenic compounds, Experentia9, 357-367(1953).
8. Eschenmoser, A. & Arigoni, D. Revisited after 50 years: the 'Stereochemlca interpretation of the biogenetic isoprene rule for the trlterpenes', Helv. Chim. Acta 88,3011-3050(2005). (Pubitemid 43051745)
9. x-hydroxyiase is a cytochrome P450-dependent monooxygenase, Proc. Natl Acad. Sci. USA 98,13595-13600 (2001). (Pubitemid 33115943)
10. Denis, J. N. et al. Highly efficient, practical approach to natural Taxol. J. Am. Chem. Soc. 110, 5917-5919 1988).
11. Mello, R., Florentino, M., Fusco, C. & Curci, R. Oxidations by methyl(trifluoromethyl)dioxirane. 2. Oxyfunctionalizationon of saturated hydrocarbons, J. Am. Chem. Soc. 111, 6749-6757 (1989).
12. Costas, M., Mehn, M. P., Jensen, M. P. & Que, L. Jr. Dioxygen activation at mononuclear nonheme iron active sites: enzymes, models, and intermediates, Chem. Rev. 104, 939-986 (2004).
13. Groves, J. T., Bonchio, M., Carofiglio, T., &, Shaiyaev, K. Rapid catalytic oxygenation of hydrocarbons by ruthenium pentafluorophenylporphyrin complexes: evidence for the involvement of a Ru(III) intermediate, J. Am. Chem. Soc. 118, 8961-8962(1996). (Pubitemid 26325164)
14. Wender, P. A., Hilinski, M. K. & Mayweg, A. V. W. Late-stage intermolecular C-H activation for lead diversification: a highly chemoselective oxyfuncťonalizaťon of the C-9 position of potent bryostatin analogues, Org, Lett. 1, 79- 82 (2005). (Pubitemid 40138316)
15. Brodsky, B. H. & Du Bois, J. Oxaziridine-mediated catalytic hydroxylation of unactivated 3° C-H bonds using hydrogen peroxide, J. Am. Chem. Soc. 127, 15391-15393(2005). (Pubitemid 41572511)
16. Yang, J., Gabriele, B., Belvedere, S., Huang, Y.&Breslow, R. Catalytic oxidations of steroid substrates by artificial cytochrome P-450 enzymes, J. Org, Chem. 67, 5057-5067 (2002). (Pubitemid 34793170)
17. Chen, M. S. & White, M. C. A predictably selective aliphatic C-H oxidation reaction for complex molecule synthesis, Science 318, 783-787 (2007).
18. Wu, Q.-X., Shi, Y.-P. & Jia, Z.-J, Eudesmane sesquiterpenoids from the Asteraceae family, Nat. Prod. Rep. 23, 699-734 (2006). (Pubitemid 44455388)
19. Cardona, L., Garcia, B., Gimenez, E. & Pedro, J. R. A shorter route to the synthesis of ('O-junenoi, isojunenol, and their coumarate esters from (--)-santonin, Tetrahedron 48, 851-860(1992).
20. Levine, S. R., Krout, M. R. &Stoltz, B. M. Catalytic enantioselective approach to the eudesmane sesquiterpenoids: total synthesis of ( + )-carissone, Org, Lett. 11, 289-292(2009).
21. Paknikar, S. K., Dhekne, V. V. & Joshl, G. D. Synthesis of 4a, 6adihydroxyeudesmane: revision of stereochemistry at C-4 of ajanol, Indian J. Chem. 15B, 86-87(1977).
22. Zhao, P.-J., Li. G.-H.& Shen, Y.-M. Newchemical constituents from the endophyte Streptomyces species LR4612 cultivated on Maytenus hookerl, Chem. Biodivers. 3, 337-342(2006).
23. Irwin, M. A. & Geissman, T. A. Sesquiterpene alcohols from Artemisia pygmaea. Phytochemistry 12, 849 852 (1973).
24. De Marino, S. et al. New sesquiterpene lactones from Laurus nobilis leaves as inhibitors of nitric oxide production, Planta Med. 71, 706-710 (2005). (Pubitemid 41306188)
25. Betancort, J. M. & Barbas, C. F. Catalytic direct asymmetric Michael reactions: taming naked aldehyde donors, Org. Lett. 3, 3737-3740 (2001). (Pubitemid 33625454)
26. Chi, Y. & Gellman, S. H. Dlphenylprolinol methyl ether: a highly enantioselective catalyst for Michael addition of aldehydes to simple enones, Org, Lett. 1, 4253-4256 (2005). (Pubitemid 41361576)
27. Chen, K., Richter, J. M. & Baran, P. S. 1,3-diol synthesis via controlled, radicalmediated C-H functionalization, J. Am. Chem. Soc. 130, 7247-7249 (2008). (Pubitemid 351813214)
28. Schreiber, J. & Eschenmoser, A. Über die relative Geschwindigkeit der Chromosäureoxydation sekundärer, aücycüscher Alkohole, Vorläufige Mitteilung, Helv. Chim. Acta 38,1529-1536 (1955).
29. Fraunhoffer, K. J., Bachovchin, D. A. & White, M. C. Hydrocarbon oxidation vs C-C bond-forming approaches for efficient syntheses of oxygenated molecules, Org. Lett. 7, 223-226 (2005). (Pubitemid 40208675)
30. Davies, H. M. L. & Manning, J. R. Catalytic C-H functionalization by meta carbenoid and nitrenoid insertion, Nature 451, 417-424 (2008). (Pubitemid 351181179)