Mining the tetraene manifold: Total synthesis of complex pyrones from Placobranchus ocellatus

Angewandte Chemie - International Edition

Volumn 44, Issue 29, 2005, Pages 4602-4606

  Miller, Aubry K ^a   Trauner, Dirk ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

Biomimetic synthesis; Electrocyclic reactions; Isomerization; Natural products synthesis; Reaction cascades

Indexed keywords

COMPLEXATION; ELECTROCHEMISTRY; ISOMERIZATION; ISOMERS; STEREOCHEMISTRY; SYNTHESIS (CHEMICAL);

ELECTROCYCLIZATION; NATURAL PRODUCTS; OCELLAPYRONE A; PYRONES;

KETONES;

BIOLOGICAL PRODUCT; BIOMIMETIC MATERIAL; PYRONE DERIVATIVE;

ANIMAL; ARTICLE; CHEMICAL MODEL; CHEMISTRY; GASTROPOD; SYNTHESIS;

ANIMALS; BIOLOGICAL PRODUCTS; BIOMIMETIC MATERIALS; GASTROPODA; MODELS, CHEMICAL; PYRONES;

EID: 22744446475     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200500488     Document Type: Article

References (31)

1. a) R. B. Woodward, R. Hoffmann, The Conservation of Orbital Symmetry, VCH, Weinheim, 1970;
2. b) E. N. Marvell, Thermal Electrocyclic Reactions, Academic Press, New York, 1980;
3. c) E. N. Marvell, J. Seubert, G. Vogt, G. Zimmer, G. Moy, J. R. Siegmann, Tetrahedron 1978, 34, 1323.
4. M. T. Davies-Colman, M. J. Garson, Nat. Prod. Rep. 1998, 15, 477, and references therein.
5. E. Manzo, M. L. Ciavatta, M. Gavagnin, E. Mollo, S. Wahidulla, G. Cimino, Tetrahedron Lett. 2005, 46, 465.
6. J. E. Moses, R. M. Adlington, R. Rodriguez, S. J. Eade, J. E. Baldwin, Chem. Commun. 2005, 13, 1687.
7. M. Cueto, L. D'Croz, J. L. Maté, A. San-Martín, J. Darias, Org. Lett. 2005, 7, 415.
8. R. Huisgen, A. Dahmen, H. Huber, J. Am. Chem. Soc. 1967, 89, 7130.
9. W. M. Bandaranayake, J. E. Banfiled, D. St. C. Black, G. D. Fallon, B. M. Gatehouse, J. Chem. Soc. Chem. Commun. 1980, 162.
10. a) C. M. Beaudry, D. Trauner, Org. Lett. 2002, 4, 2221;
11. b) J. E. Moses, J. E. Baldwin, R. Marquez, R. M. Adlington, A. R. Cowley, Org. Lett. 2002, 4, 3731.
12. a) K. C. Nicolaou, N. A. Petasis, J. Uenishi, R. E. Zipkin, J. Am. Chem. Soc. 1982, 104, 5555;
13. b) K. A. Parker, Y. H. Lim, J. Am. Chem. Soc. 2004, 126, 15968;
14. M. F. Jacobsen, J. E. Moses, R. M. Adlington, J. E. Baldwin, Org. Lett. 2005, 7, in press.
15. a) A. K. Miller, D. Trauner, Angew. Chem. 2003, 115, 567;
16. Angew. Chem. Int. Ed. 2003, 42, 549;
17. b) A. K. Miller, M. R. Banghart, J. M. Suh, D. Trauner, Tetrahedron 2003, 59, 8919;
18. c) A. K. Miller, D. H. Byun, C. M. Beaudry, D. Trauner, Proc. Natl. Acad. Sci. USA 2004, 101, 12019.
19. G. Dahmann, R. W. Hoffman, Liebigs Ann. Chem. 1994, 837.
20. S. P. H. Mee, V. Lee, J. Baldwin, Angew. Chem. 2004, 116, 1152;
21. Angew. Chem. Int. Ed. 2004, 43, 1132.
22. G. Liang, A. K. Miller, D. Trauner, Org. Lett. 2005, 7, 819.
23. The outcome of this isomerization was found to be strongly dependent on the conditions employed; for example, tetraene 14 underwent isomerization under microwave irradiation (PhMe, 150°C, 20 min) to afford 9,10-deoxytridachione (1) and ocellapyrone A (5) in approximately equal amounts. (Chemical Equation Presented)
24. In the reported isolation of bicyclo[4.2.0]octadiene 5 and endoperoxide 7 (Ref. [3]), the relative structure of ocellapyrone A was "... mainly determined on the basis of NOE difference and NOESY experiments recorded on the peroxide derivative [= ocellapyrone B]".
25. Independent confirmation of the structure of 5 was obtained by conversion into the corresponding endo peroxide, whose structure was determined by X-ray crystallographic analysis. CCDC-269389 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.
26. A. Mordini, S. Pecchi, G. Capozzi, A. Capperucci, A. Degl'Innocenti, G. Reginato, A. Ricci, J. Org. Chem. 1994, 59, 4784.
27. J. E. Barbarow, A. K. Miller, D. Trauner, submitted.
28. M. Suzuki, H. Ohtake, Y. Kameya, N. Hamanaka, R. Noyori, J. Org. Chem. 1989, 54, 5292.
29. S. Nitz, H. Kollmannsberger, M. H. Spraul, F. Drawert, Phytochemistry 1989, 28, 3051.
30. CCDC-269388 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.
31. In our previous reports on photodeoxytridachione (Ref. [10a, b]), we erroneously reported the 6π electrocyclization of tetraenoic ester 21 to afford cyclohexadiene 22. The "upfield shift" of a vinyl proton (δ = 2.93 ppm) was rationalized with an anisotropic effect exerted by the nearby ester carbonyl group. In fact, double-bond isomerization followed by a stereoselective 8π-6π electrocyclization cascade had taken place. Therefore, the product of this very high-yielding and stereoselective reaction is reassigned as 23. The structure of 23 was confirmed by reduction of the ester function to a primary alcohol followed by acid-catalyzed ring closure to the caged tricyclic compound 24. (DIBAH = diisobutylaluminum hydride.) (Chemical Equation Presented)