The correct structure of aquatolide - Experimental validation of a theoretically-predicted structural revision

Journal of the American Chemical Society

Volumn 134, Issue 45, 2012, Pages 18550-18553

  Lodewyk, Michael W ^a   Soldi, Cristian ^a   Jones, Paul B ^b   Olmstead, Marilyn M ^a   Rita, Juan ^c   Shaw, Jared T ^a   Tantillo, Dean J ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b WAKE FOREST UNIVERSITY   (United States)

^c UNIVERSITAT DE LES ILLES BALEARS   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

EXPERIMENTAL VALIDATIONS; NATURAL SOURCES; NMR ANALYSIS;

CRYSTALLOGRAPHY; QUANTUM CHEMISTRY;

CHEMICAL ANALYSIS;

AQUATOLIDE; SESQUITERPENOID; UNCLASSIFIED DRUG;

ARTICLE; CALCULATION; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL BOND; CHEMICAL STRUCTURE; CONTROLLED STUDY; CRYSTALLOGRAPHY; CYCLIZATION; HYDROGEN BOND; PROTON NUCLEAR MAGNETIC RESONANCE; QUANTUM CHEMISTRY;

ASTERACEAE; CRYSTALLOGRAPHY, X-RAY; MAGNETIC RESONANCE SPECTROSCOPY; MODELS, MOLECULAR; MOLECULAR STRUCTURE; REFERENCE STANDARDS; SESQUITERPENES;

EID: 84869458987     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja3089394     Document Type: Article

References (32)

1. San Feliciano, A.; Medarde, M.; Miguel del Corral, J. M.; Aramburu, A.; Gordaliza, M.; Barrero, A. F. Tetrahedron Lett. 1989, 30, 2851
2. Nouri, D. H.; Tantillo, D. J. Org. Biomol. Chem. 2012, 10, 5514
3. Nouri, D. H.; Tantillo, D. J. Curr. Org. Chem. 2006, 10, 2055
4. For the only example, to our knowledge, of a sesquiterpenoid containing a [2]ladderane substructure (confirmed by crystallography), see: Fedorov, S. N.; Radchenko, O. S.; Shubina, L. K.; Kalinovsky, A. I.; Gerasimenko, A. V.; Popov, D. Y.; Stonik, V. A. J. Am. Chem. Soc. 2001, 123, 504
5. Quasdorf, K. W.; Huters, A. D.; Lodewyk, M. W.; Tantillo, D. J.; Garg, N. K. J. Am. Chem. Soc. 2012, 134, 1396
6. Lodewyk, M. W.; Siebert, M. R.; Tantillo, D. J. Chem. Rev. 2012, 112, 1839
7. Lodewyk, M. W.; Tantillo, D. J. J. Nat. Prod. 2011, 74, 1339
8. http://cheshirenmr.info (accessed Sept 14, 2012).
9. 1H coupling constant calculations, see: Bally, T.; Rablen, P. R. J. Org. Chem. 2011, 76, 4818
10. San Feliciano, A.; Barrero, A. F.; Medarde, M.; Miguel del Corral, J. M.; Aramburu, A. Tetrahedron Lett. 1985, 26, 2369
11. San Feliciano, A.; Barrero, A. F.; Medarde, M.; Miguel del Corral, J. M.; Aramburu, A. Tetrahedron 1985, 41, 5711
12. Trost, B. M.; Burns, A. C.; Bartlett, M. J.; Tautz, T.; Weiss, A. J. Am. Chem. Soc. 2012, 134, 1474
13. Wender, P. A.; Ihle, N. C.; Correia, C. R. D. J. Am. Chem. Soc. 1988, 110, 5904
14. Paquette, L. A.; Tae, J.; Arrington, M. P.; Sadoun, A. H. J. Am. Chem. Soc. 2000, 122, 2742
15. Limanto, J.; Snapper, M. L. J. Am. Chem. Soc. 2000, 122, 8071
16. Kraft, M. E.; Cheung, Y.-Y.; Juliano-Capucao, C. A. Synthesis 2000, 1020
17. Kraft, M. E.; Cheung, Y.-Y.; Abboud, K. A. J. Org. Chem. 2001, 66, 7443
18. Liang, Y.; Jiang, X.; Yu, Z.-X. Chem. Commun. 2011, 47, 6659
19. Liang, Y.; Jiang, X.; Fu, X.-F.; Ye, S.; Wang, T.; Yuan, J.; Wang, Y.; Yu, Z.-X. Chem. - Asian J. 2012, 7, 593
20. Srinivasan, R.; Carlough, K. H. J. Am. Chem. Soc. 1967, 89, 4932
21. Liu, R. S. H.; Hammond, G. S. J. Am. Chem. Soc. 1967, 89, 4936
22. Gleiter, R.; Sander, W. Angew. Chem., Int. Ed. Engl. 1985, 24, 566
23. Dilling, W. L. Chem. Rev. 1966, 66, 373
24. Notably, asteriscanolide may be related to the corrected structure of aquatolide as a product of its fragmentation or as a product of incomplete [2 + 2] reaction, photochemical or not (we thank Dr. Yong Liang of UCLA for sharing the results of his preliminary calculations on these possibilities). Also see: El Dahmy, S.; Jakupovic, J.; Bohlmann, F.; Sarg, T. M. Tetrahedron 1985, 41, 309
25. The synthesis of a related bicyclo[2.1.1]hexane system bearing a gem -dimethyl group and a fused lactone unit was described previously, but NMR data for this compound were not provided. See: Meinwald, J.; Gassman, P. G.; Hurst, J. J. J. Am. Chem. Soc. 1962, 84, 3722
26. Bohlmann, F.; Jakupovic, J.; Warning, U.; Grenz, M.; Chau-Thi, T. V.; King, R. M.; Robinson, H. Bull. Soc. Chim. Belg. 1986, 95, 707
27. Schenk, H.; Driessen, R. A. J.; de Gelder, R.; Goubitz, K.; Nieboer, H.; Brüggemann-Rotgans, I. E. M.; Diepenhorst, P. Croat. Chem. Acta 1999, 72, 593
28. Barfield, M. Magn. Reson. Chem. 2003, 41, 344
29. Wiberg, K. B.; Lampman, G. M.; Ciula, R. P.; Connor, D. S.; Schertler, P.; Lavanish, J. Tetrahedron 1965, 21, 2749
30. Wiberg, K. B.; Lowry, B. R.; Nist, B. J. J. Am. Chem. Soc. 1962, 84, 1594
31. Nicolaou, K. C.; Snyder, S. A. Angew. Chem., Int. Ed. 2005, 44, 1012
32. Molinski, T. F. Curr. Opin. Biotechnol. 2010, 21, 819