Zirconocene-catalyzed reactions of alkenyl-substituted enol ethers

Angewandte Chemie - International Edition

Volumn 45, Issue 38, 2006, Pages 6362-6365

  Barluenga, José ^a   Álvarez Rodrigo, Lucía ^a   Rodríguez, Félix ^a   Fañanás, Francisco J ^a  

^a UNIVERSITY OF OVIEDO   (Spain)

Author keywords

Grignard reagents; Homogeneous catalysis; Rearrangement; Synthetic methods; Zirconium

Indexed keywords

CATALYSIS; REACTION KINETICS; SUBSTITUTION REACTIONS; SYNTHESIS (CHEMICAL); ZIRCONIUM;

GRIGNARD REAGENTS; HOMOGENEOUS CATALYSIS; REARRANGEMENT; SYNTHETIC METHODS;

ETHERS;

EID: 33749249022     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200601959     Document Type: Article

References (54)

1. a) New Aspects of Zirconium-Containing Organic Compounds, Topics in Organomet. Chem., Vol. 10 (Ed.: I. Marek), Springer, Berlin, 2005;
2. b) Titanium and Zirconium in Organic Synthesis (Ed.: I. Marek), Wiley-VCH, Weinheim, Germany, 2002.
3. For some representative examples, see: a) J. Schwartz, J. A. Labinger, Angew. Chem. 1976, 88, 402;
4. Angew. Chem. Int. Ed. Engl. 1976, 15, 333;
5. b) C. A. Bertelo, J. Schwartz, J. Am. Chem. Soc. 1976, 98, 262;
6. c) D. W. Hart, T. F. Blackburn, J. Schwartz, J. Am. Chem. Soc. 1975, 97, 679;
7. d) D. W. Hart, J. Schwartz, J. Am. Chem. Soc. 1974, 96, 8115.
8. E. Negishi, T. Takahashi, Acc. Chem. Res. 1994, 27, 124, and references cited therein.
9. Zirconocene complexes are known to catalyze polymerization reactions; for some other interesting zirconocene-catalyzed reactions, see: a) Y. Ikeuchi, T. Taguchi, Y. Hanzawa, J. Org. Chem. 2005, 70, 4354;
10. b) J. Terao, S. A. Begum, A. Oda, N. Kambe, Synlett 2005, 1783;
11. c) V. Gandon, P. Bertus, J. Szymoniak, Eur. J. Org. Chem. 2001, 3677;
12. d) P. Wipf, S. Ribe, Org. Lett. 2001, 3, 1503;
13. e) Y. Ura, R. Hara, T. Takahashi, Chem. Commun. 2000, 875;
14. f) F. Grepioni, S. Grilli, G. Martelli, D. Saoia, J. Org. Chem. 1999, 64, 3679;
15. g) Y. Yamamura, M. Mori, Tetrahedron Lett. 1999, 40, 3221;
16. h) K. Kasai, Y. Liu, R. Hara, T. Takahashi, Chem. Commun. 1998, 1989;
17. i) D. B. Millward, R. M. Waymouth, Organometallics 1997, 16, 1153;
18. j) G. Dawson, C. A. Durrant, G. G. Kirk, R. J. Whitby, R. V. H. Jones, M. C. H. Standen, Tetrahedron Lett. 1997, 38, 2335;
19. k) N. Uesaka, M. Mori, K. Okamura, T. Date, J. Org. Chem. 1994, 59, 4542;
20. l) T. Takahashi, D. Y. Kondakov, N. Suzuki, Organometallics 1994, 13, 3411;
21. m) D. P. Lewis, P. M. Muller, R. J. Whitby, R. V. H. Jones, Tetrahedron Lett. 1991, 32, 6797.
22. For some recent papers, see: a) Z. Tan, E. Negishi, Angew. Chem. 2004, 116, 2971;
23. Angew. Chem. Int. Ed. 2004, 43, 2911;
24. b) E. Negishi, Z. Tan, B. Liang, T. Novak, Proc. Natl. Acad. Sci. USA 2004, 101, 5782;
25. c) S. Huo, J. Shi, E. Negishi, Angew. Chem. 2002, 114, 2245;
26. Angew. Chem. Int. Ed. 2002, 41, 2141.
27. a) R. R. Cesati III, J. de Armas, A. H. Hoveyda, Org. Lett. 2002, 4, 395;
28. b) J. de Armas, A. H. Hoveyda, Org. Lett. 2001, 3, 2097;
29. c) J. de Armas, S. P. Kolis, A. H. Hoveyda, J. Am. Chem. Soc. 2000, 122, 5977;
30. d) A. H. Hoveyda in Titanium and Zirconium in Organic Synthesis (Ed.: I. Marek), Wiley-VCH, Weinheim, Germany, 2002, p. 180.
31. a) J. Barluenga, F. Rodríguez, L. Álvarez-Rodrigo, F. J. Fañanás, Chem. Soc. Rev. 2005, 34, 762;
32. b) J. Barluenga, A. Fernández, L. Álvarez-Rodrigo, F. Rodríguez, F. J. Fañanás, Synlett 2005, 2513;
33. c) J. Barluenga, L. Álvarez-Rodrigo, F. Rodríguez, F. J. Fañanás, Angew. Chem. 2004, 116, 4022;
34. Angew. Chem. Int. Ed. 2004, 43, 3932;
35. d) J. Barluenga, F. Rodríguez, L. Álvarez-Rodrigo, J. M. Zapico, F. J. Fañanás, Chem. Eur. J. 2004, 10, 109;
36. e) J. Barluenga, F. Rodríguez, L. Álvarez-Rodrigo, F. J. Fañanás, Chem. Eur. J. 2004, 10, 101.
37. a) N. Chinkov, A. Levin, I. Marek, Angew. Chem. 2006, 118, 479;
38. Angew. Chem. Int. Ed. 2006, 45, 465;
39. b) I. Marek, N. Chinkov, A. Levin, Synlett 2006, 501;
40. c) S. Farhat, I. Zouev, I. Marek, Tetrahedron 2004, 60, 1329;
41. d) N. Chinkov, S. Majumdar, I. Marek, J. Am. Chem. Soc. 2003, 125, 13 258;
42. e) S. Farhat, I. Marek, Angew. Chem. 2002, 114, 1468;
43. Angew. Chem. Int. Ed. 2002, 41, 1410;
44. f) N. Chinkov, H. Chechik, S. Majumdar, A. Liard, I. Marek, Synthesis 2002, 2473;
45. g) N. Chinkov, S. Majumdar, I. Marek, J. Am. Chem. Soc. 2002, 124, 10 282;
46. h) A. Liard, J. Kaftanov, H. Chechik, S. Farhat, N. Morlender-Vais, C. Averbuj, I. Marek, J. Organomet. Chem. 2001, 624, 26;
47. i) A. Liard, I. Marek, J. Org. Chem. 2000, 65, 7218.
48. For interesting zirconocene-induced cocyclization-elimination reactions, see: a) D. R. Owen, R. J. Whitby, Synthesis 2005, 2061;
49. b) M. Kotora, G. Gao, Z. Li, T. Takahashi, Tetrahedron Lett. 2000, 41, 7905;
50. c) D. B. Millward, R. M. Waymouth, Organometallics 1997, 16, 1153.
51. The reaction led to a complex mixture of unidentified compounds when less polar solvents, such as toluene or hexane, were used. Similar variations on the diastereoselectivity by changing the solvent (from diethyl ether to THF) have been observed in related works; this solvent effect has been attributed to the chelation between the zirconium center and the solvent; for details, see: A. F. Houri, M. T. Didiuk, Z. Xu, N. R. Horan, A. H. Hoveyda, J. Am. Chem. Soc. 1993, 115, 6614.
52. 3 has led to important improvements in related processes; see for example ref. [4k]. The role played by the phosphine moiety in these processes is unclear; however, we hypothesize the possibility of a stabilization of sixteen-electron zirconocene complexes such as 9 and/or 10 (see Scheme 4). As these complexes are the real catalytic species of the reaction, their stabilization by coordination with the phosphine allows a longer half-life time of the catalyst and so, a lower zirconium loading is possible.
53. Alternatively, a similar mechanism that involves the formation of a zirconate species by addition of PrMgCl to 3a followed by Mg-Zr exchange, elimination of Mg alkoxide, further reaction with another molecule of PrMgCl, and a second transmetalation step to form 11 and 9 might also be suggested; see ref. [6].
54. Starting enol ethers used in this work are very readily available on a large scale by Pd-catalyzed O-vinylation of the corresponding homoallyl alcohol; see: K. F. W. Hekking, F. L. van Delft, F. P. J. T. Rutjes, Tetrahedron 2003, 59, 6751.