Palladium-Catalyzed Decarbonylative Dehydration for the Synthesis of α-Vinyl Carbonyl Compounds and Total Synthesis of (-)-Aspewentins A, B, and C

Angewandte Chemie - International Edition

Volumn 54, Issue 40, 2015, Pages 11800-11803

  Liu, Yiyang ^a   Virgil, Scott C ^a   Grubbs, Robert H ^a   Stoltz, Brian M ^a  

^a California Institute of Technology   (United States)

Author keywords

enantioselectivity; natural products; olefination; palladium; total synthesis

Indexed keywords

CATALYSIS; DEHYDRATION; ENANTIOSELECTIVITY; PALLADIUM; SYNTHESIS (CHEMICAL);

ASYMMETRIC ALLYLIC ALKYLATIONS; ENANTIOSELECTIVE; ENANTIOSELECTIVE TOTAL SYNTHESIS; NATURAL PRODUCTS; OLEFINATION; PALLADIUM-CATALYZED; QUATERNARY STEREOCENTERS; TOTAL SYNTHESIS;

CARBONYL COMPOUNDS;

EID: 84942366983     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201505161     Document Type: Article

References (37)

1. K. Bernauer, G. Englert, W. Vetter, E. Weiss, Helv. Chim. Acta 1969, 52, 1886-1905;
2. R. E. Moore, C. Cheuk, G. M. L. Patterson, J. Am. Chem. Soc. 1984, 106, 6456-6457;
3. T. Masuda, K. Masuda, S. Shiragami, A. Jitoe, N. Nakatani, Tetrahedron 1992, 48, 6787-6792;
4. 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.
5. Y. Nishimoto, H. Ueda, M. Yasuda, A. Baba, Angew. Chem. Int. Ed. 2012, 51, 8073-8076;
6. Angew. Chem. 2012, 124, 8197-8200.
7. A. Chieffi, K. Kamikawa, J. Åhman, J. M. Fox, S. L. Buchwald, Org. Lett. 2001, 3, 1897-1900;
8. J. Huang, E. Bunel, M. M. Faul, Org. Lett. 2007, 9, 4343-4346;
9. A. M. Taylor, R. A. Altman, S. L. Buchwald, J. Am. Chem. Soc. 2009, 131, 9900-9901.
10. M. Nakamura, K. Endo, E. Nakamura, Org. Lett. 2005, 7, 3279-3281;
11. K. Endo, T. Hatakeyama, M. Nakamura, E. Nakamura, J. Am. Chem. Soc. 2007, 129, 5264-5271;
12. T. Fujimoto, K. Endo, H. Tsuji, M. Nakamura, E. Nakamura, J. Am. Chem. Soc. 2008, 130, 4492-4496.
13. M. Yamaguchi, T. Tsukagoshi, M. Arisawa, J. Am. Chem. Soc. 1999, 121, 4074-4075;
14. M. Arisawa, C. Miyagawa, S. Yoshimura, Y. Kido, M. Yamaguchi, Chem. Lett. 2001, 1080-1081.
15. R. Tanikaga, H. Sugihara, K. Tanaka, A. Kaji, Synthesis 1977, 299-301.
16. C. J. Kowalski, J.-S. Dung, J. Am. Chem. Soc. 1980, 102, 7950-7951;
17. D. L. J. Clive, C. G. Russell, S. C. Suri, J. Org. Chem. 1982, 47, 1632-1641.
18. T. Nozoye, Y. Shibanuma, T. Nakai, Y. Hatori, Chem. Pharm. Bull. 1988, 36, 4980-4985.
19. A. I. Meyers, R. Hanreich, K. T. Wanner, J. Am. Chem. Soc. 1985, 107, 7776-7778;
20. H. Kawashima, Y. Kaneko, M. Sakai, Y. Kobayashi, Chem. Eur. J. 2014, 20, 272-278.
21. M. Pfau, G. Revial, A. Guingant, J. D'Angelo, J. Am. Chem. Soc. 1985, 107, 273-274.
22. J. T. Mohr, D. C. Behenna, A. M. Harned, B. M. Stoltz, Angew. Chem. Int. Ed. 2005, 44, 6924-6927;
23. Angew. Chem. 2005, 117, 7084-7087.
24. Y. Liu, K. E. Kim, M. B. Herbert, A. Fedorov, R. H. Grubbs, B. M. Stoltz, Adv. Synth. Catal. 2014, 356, 130-136.
25. I. G. J. de Avellar, F. W. Vierhapper, Tetrahedron 2000, 56, 9957-9965.
26. F.-P. Miao, X.-R. Liang, X.-H. Liu, N.-Y. Ji, J. Nat. Prod. 2014, 77, 429-432.
27. The enantioselective Michael addition does not work for 1-tetralone substrates. For details, see:, J. d'Angelo, D. Desmaële, F. Dumas, A. Guingant, Tetrahedron: Asymmetry 1992, 3, 459-505.
28. Allergan, Inc. Patent WO2005/58301A1, 2005.
29. M. L. Brown, H. A. Eidam, M. Paige, P. J. Jones, M. K. Patel, Bioorg. Med. Chem. 2009, 17, 7056-7063.
30. A. N. Marziale, D. C. Duquette, R. A. Craig II, K. E. Kim, M. Liniger, Y. Numajiri, B. M. Stoltz, Adv. Synth. Catal. 2015, 357, 2238-2245.
31. An alternative route from the allyl ketone 12 to vinyl ketone 17 involves isomerization of the double bond to the internal position followed by ethenolysis. While the isomerization (i.e., 12 → SI-17) proceeded smoothly using the protocol developed by Nishida and co-workers (, M. Arisawa, Y. Terada, M. Nakagawa, A. Nishida, Angew. Chem. Int. Ed. 2002, 41, 4732-4734;
32. Angew. Chem. 2002, 114, 4926-4928) to afford the internal olefin SI-17, attempts at ethenolysis of the resulting internal olefin were unsuccessful, likely a result of the steric bulk at the adjacent quaternary center. See the Supporting Information for details.
33. Spectroscopic data (1H and 13C NMR) and exact mass of the synthetic compound matches those of natural (+)-aspewentin B. The optical rotation, however, is significantly different (synthetic compound: [α]D25 -90.5 (c 0.20, MeOH, 98 % ee); natural product: [α]D20 +23.3 (c 0.20, MeOH)). HPLC analysis showed the synthetic compound to be of 98 % ee. Based on the stereoselectivity of the Pd-PHOX catalyst in previous examples, we reasoned that the absolute configuration of our synthetic compound is opposite to that of the natural product, and thus the sign of optical rotation is correct. The difference in magnitude may arise from the possibility that the natural product is a scalemic mixture (i.e. not enantiopure). For a review on non-enantiopure natural products, see:, J. M. Finefield, D. H. Sherman, M. Kreitman, R. M. Williams, Angew. Chem. Int. Ed. 2012, 51, 4802-4836;
34. Angew. Chem. 2012, 124, 4886-4920. Another possibility is that the isolated natural product contained a small amount of impurity which had a large effect on the optical rotation.
35. G. Quandt, G. Höfner, K. T. Wanner, Bioorg. Med. Chem. 2013, 21, 3363-3378.
36. P. N. Carlsen, T. J. Mann, A. H. Hoveyda, A. J. Frontier, Angew. Chem. Int. Ed. 2014, 53, 9334-9338;
37. Angew. Chem. 2014, 126, 9488-9492.