Pronounced steric effects of substituents in the Nazarov cyclization of aryl dienyl ketones

Angewandte Chemie - International Edition

Volumn 47, Issue 34, 2008, Pages 6379-6383

  Marcus, Andrew P ^b   Lee, Amy S ^b   Davis, Rebecca L ^a   Tantillo, Dean J ^a   Sarpong, Richmond ^b  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

Annulation; Density functional calculations; Dienones; Electrocyclic reactions; Nazarov cyclization

Indexed keywords

KETONES;

ANNULATION; DENSITY FUNCTIONAL CALCULATIONS; DIENONES; ELECTROCYCLIC REACTIONS; NAZAROV CYCLIZATION;

ORGANIC COMPOUNDS;

FUSED HETEROCYCLIC RINGS; GLYCOSIDE; KETONE; TETRAPETALONE A;

ARTICLE; CHEMISTRY; CYCLIZATION; STEREOISOMERISM; SYNTHESIS;

CYCLIZATION; GLYCOSIDES; HETEROCYCLIC COMPOUNDS WITH 4 OR MORE RINGS; KETONES; STEREOISOMERISM;

EID: 52049083287     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200801542     Document Type: Article

References (44)

1. For pertinent reviews, see: a) A. J. Frontier, C. Collison, Tetrahedron 2005, 61, 7577-7606;
2. b) M. A. Tius, Eur. J. Org. Chem. 2005, 2193-2206;
3. c) H. Pellissier, Tetrahedron 2005, 61, 6479-6517;
4. d) M. Harmata, Chemtracts 2004, 17, 416-435.
5. For a recent account featuring allenyl vinyl ketones, see: M. A. Tius, Acc. Chem. Res. 2003, 36, 284-290.
6. For examples of tandem reactions that involve capture of the Nazarov intermediate, see: a) M. Janka, W. He, I. E. Haedicke, F. R. Fronczek, A. J. Frontier, R. Eisenberg, J. Am. Chem. Soc. 2006, 128, 5312-5313;
7. b) Y. Wang, B. D. Schill, A. M. Arif, F. G. West, Org. Lett. 2003, 5, 2747-2750;
8. c) G. Liang, Y. Xu, I. B. Seiple, D. Trauner, J. Am. Chem. Soc. 2006, 128, 11022-11023.
9. a) T. Komoda, Y. Sugiyama, N. Abe, M. Imachi, H. Hirota, H. Koshino, A. Hirota, Tetrahedron Lett. 2003, 44, 7417-7419;
10. b) T. Komoda, M. Kishi, N. Abe, Y. Sugiyama, A. Hirota, Biosci. Biotechnol. Biochem. 2004, 68, 903-908.
11. The earlier report from Wang and Porco of an advanced tetracyclic intermediate has recently been retracted, see: a) X. Wang, J. A. Porco, Angew. Chem. 2006, 118, 6759;
12. Angew. Chem. Int. Ed. 2006, 45, 6607;
13. b) X. Wang, J. A. Porco, Angew. Chem. 2005, 117, 3127-3131;
14. Angew. Chem. Int. Ed. 2005, 44, 3067-3071.
15. For details, see the Supporting Information.
16. Similarly, i was unreactive under the standard conditions, whereas ii provided the corresponding indanone in 58% yield as a 92:8 mixture of diastereomers. (Chemical Equation Presented)
17. The work detailed in this manuscript was presented by RS and APM in poster sessions at a Gordon Research Conference (July 16-21, 2006, Organic Reactions and Processes, Bryant University) and 232nd ACS National Meeting (San Francisco, CA, United States, Sept. 10-14, 2006, ORGN-523), respectively.
18. E. A. Braude, W. F. Forbes, J. Chem. Soc. 1953, 2208-2216.
19. G. Liang, S. N. Gradl, D. Trauner, Org. Lett. 2003, 5, 4931-4934.
20. W. He, I. R. Herrick, T. A. Atesin, P. A. Caruana, C. A. Kellenberger, A. J. Frontier, J. Am. Chem. Soc. 2008, 130, 1003-1011.
21. An electron-rich aryl fragment in the aryl dienyl ketone substrate is important and consistent with recent findings, see: J. A. Malona, J. M. Colbourne, A. J. Frontier, Org. Lett. 2006, 8, 5661-5664.
22. This initial study is restricted to alkyl substituents.
23. a) For a detailed discussion, see the recent reviews on this subject (references [1a-c]);
24. -1 lower in energy than the s-cis form;
25. c) See the Supporting Information for details and additional related examples.
26. Cyclization is expected to be the rate-determining step of the entire transformation. For a discussion, see reference [1].
27. For computational analyses of other variants of the classic Nazarov reaction, see: a) M. Harmata, P. R. Schreiner, D. R. Lee, P. L. Kirchhoefer, J. Am. Chem. Soc. 2004, 126, 10954-10957;
28. b) A. Cavalli, M. Masetti, M. Recanatini, C. Prandi, A. Guarna, E. G. Occhiato, Chem. Eur. J. 2006, 12, 2836-2845;
29. c) O. Nieto Faza, C. S. López, R. Álvarez, A. R. de Lera, Chem. Eur. J. 2004, 10, 4324-4333.
30. a) A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652;
31. b) A. D. Becke, J. Chem. Phys. 1993, 98, 1372-1377;
32. c) C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789;
33. d) P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994, 98, 11623-11627;
34. e) These calculations were run by using Gaussian03 (full citation can be found in the Supporting Information, along with additional details on these calculations, including test calculations in toluene). Free energy barriers include entropy corrections computed for 25°C.
35. 3-complexed reactants (see Figure 1 and the Supporting Information). Twisting of 2,4-dialkyl 2-trans-4-trans pentadienals has been studied: H. Ogawa, Y. Taketugu, T. Imoto, Y. Taniguchi, H. Kato, Tetrahedron Lett. 1979, 20, 3457-3460.
36. [6]
37. [6]
38. [6]
39. Presumably, the exocyclic double bond isomerizes to an endocyclic position under the reaction conditions.
40. [19]
41. Barriers for several other systems have been calculated ahead of experimental testing. See the Supporting Information for details.
42. [27] at 70°C to provide cyclopentenone 28 (via 27) in 61% yield [Eq. (7)]. Efforts to understand the underlying selectivity principles for these latter transformations are underway.
43. 2), γ-unsubstituted aryl dienyl ketone were also described in reference [11] (see Table 7 therein).
44. S. E. Denmark, G. A. Hite, Helv. Chim. Acta 1988, 71, 195-208.