Air-stable {(C5H5)Co} catalysts for [2+2+2] cycloadditions

Angewandte Chemie - International Edition

Volumn 48, Issue 10, 2009, Pages 1810-1813

  Geny, Anaïs ^a   Agenet, Nicolas ^a   Iannazzo, Laura ^a   Malacria, Max ^a   Aubert, Corinne ^a   Gandon, Vincent ^a  

^a SORBONNE UNIVERSITÉ   (France)

Author keywords

Alkynes; Cobalt; Cycloaddition; Cyclopentadienyl ligands; Nitrogen heterocycles

Indexed keywords

ACETYLENE; BENZENE; CARBON MONOXIDE; CATALYSIS; CATALYSTS; COBALT; CYANIDES; CYCLOADDITION; LIGANDS; MICROWAVE IRRADIATION; OLEFINS;

AIR STABLES; ALKYNES; CO LIGANDS; CYCLOADDITIONS; CYCLOHEXADIENES; CYCLOPENTADIENYL COMPLEXES; CYCLOPENTADIENYL LIGANDS; FUMARATE; MICROWAVE CONDITIONS; NITROGEN HETEROCYCLES;

COBALT COMPOUNDS;

EID: 61349084243     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200806001     Document Type: Article

References (66)

1. For reviews on [2+2+2] cycloaddition reactions, see: a) K. P. C. Vollhardt, Angew. Chem. 1984, 96, 525;
2. Angew. Chem. Int. Ed. Engl. 1984, 23, 539;
3. b) J. Varela, C. Saá, Chem. Rev. 2003, 103, 3787;
4. c) Y. Yamamoto, Curr. Org. Chem. 2005, 9, 503;
5. d) V. Gandon, C. Aubert, M. Malacria, Curr. Org. Chem. 2005, 9, 1699;
6. e) S. Kotha, E. Brahmachary, K. Lahiri, Eur. J. Org. Chem. 2005, 4741;
7. f) V. Gandon, C. Aubert, M. Malacria, Chem. Commun. 2006, 2209;
8. g) P. R. Chopade, J. Louie, Adv. Synth. Catal. 2006, 348, 2307;
9. h) N. Agenet, V. Gandon, O. Buisine, F. Slowinski, C. Aubert, M. Malacria in Organic Reactions, Vol. 68 (Ed.: T. V. RajanBabu), Wiley, Hoboken, 2007, pp. 1-302;
10. i) B. Heller, M. Hapke, Chem. Soc. Rev. 2007, 36, 1085;
11. j) K. Tanaka, Synlett 2007, 1977;
12. k) K. Tanaka, Chem. Asian J. 2008, DOI: 10.1002/asia.200800378;
13. l) W. Hess, J. Treutwein, G. Hilt, Synthesis 2008, 3537;
14. m) J. Varela, C. Saá, Synlett 2008, 2571;
15. n) T. Shibata, K. Tsuchikama, Org. Biomol. Chem. 2008, 6, 1317;
16. o) C. J. Scheuermann née Taylor, B. D. Ward, New J. Chem. 2008, 32, 1850.
17. Non-cyclopentadienyl cobalt complexes can also catalyze [2+2+2] cycloaddition. For example, see: a) F. Slowinski, C. Aubert, M. Malacria, Adv. Synth. Catal. 2001, 343, 64;
18. b) M.-S. Wu, M. Shanmugasundaram, C.-H. Cheng, Chem. Commun. 2003, 718;
19. c) M.-S. Wu, D. K. Rayabarapu, C.-H. Cheng, Tetrahedron 2004, 60, 10005;
20. d) G. Hilt, T. Vogler, W. Hess, F. Galbiati, Chem. Commun. 2005, 1474;
21. e) N. Saino, F. Amemiya, E. Tanabe, K. Kase, S. Okamoto, Org. Lett. 2006, 8, 1439;
22. f) L. Doszczak, P. Fey, R. Tacke, Synlett 2007, 753;
23. g) M. W. Büttner, J. B. Nätscher, C. Burschka, R. Tacke, Organometallics 2007, 26, 4835;
24. h) L. Doszczak, R. Tacke, Organometallics 2007, 26, 5722;
25. i) K. Kase, A. Goswami, K. Ohtaki, E. Tanabe, N. Saino, S. Okamoto, Org. Lett. 2007, 9, 931;
26. j) G. Hilt, W. Hess, K. Harms, Synthesis 2008, 75;
27. k) G. Hilt, A. Paul, K. Harms, J. Org. Chem. 2008, 73, 5187.
28. For some recent examples, see: a) M. Kögl, L. Brecker, R. Warrass, J. Mulzer, Eur. J. Org. Chem. 2008, 2714;
29. b) M. Kögl, L. Brecker, R. Warrass, J. Mulzer, Angew. Chem. 2007, 119, 9480;
30. Angew. Chem. Int. Ed. 2007, 46, 9320;
31. c) N. Agenet, J.-H. Mirebeau, M. Petit, R. Thouvenot, V. Gandon, M. Malacria, C. Aubert, Organometallics 2007, 26, 819.
32. For some recent examples, see: a) B. Heller, A. Gutnov, C. Fischer, H.-J. Drexler, A. Spannenberg, D. Redkin, C. Sunder-mann, B. Sundermann, Chem. Eur. J. 2007, 13, 1117;
33. b) A. Bouet, B. Heller, C. Papamicaël, G. Dupas, S. Oudeyer, F. Marsais, V. Levacher, Org. Biomol. Chem. 2007, 5, 1397;
34. c) B. Heller, D. Redkin, A. Gutnov, C. Fischer, W. Bonrath, R. Karge, M. Hapke, Synthesis 2008, 69.
35. For some recent examples, see: a) S. Amslinger, C. Aubert, V. Gandon, M. Malacria, E. Paredes, K. P. C. Vollhardt, Synlett 2008, 2056;
36. b) V. Gandon, C. Aubert, M. Malacria, K. P. C. Vollhardt, Chem. Commun. 2008, 1599;
37. c) C. Aubert, P. Betsch-mann, M. J. Eichberg, V. Gandon, T. J. Heckrodt, J. Lehmann, M. Malacria, B. Masjost, E. Paredes, K. P. C. Vollhardt, G. D. Whitener, Chem. Eur. J. 2007, 13, 7443;
38. d) A. Geny, D. Lebceuf, G. Rouquié, K. P. C. Vollhardt, M. Malacria, V. Gandon, C. Aubert, Chem. Eur. J. 2007, 13, 5408.
39. 2], see data sheet of suppliers;
40. b) For [CpCo-(cod)], see: P. L. Pauson, M. V. Chelliah, e-EROS 2008, DOI:10.1002/047084289X.rc289.pub2;
41. 2], see: V. Gandon, C. Aubert, e-EROS 2008, DOI: 10.1002/047084289X.rn00943.pub2.
42. The use of functionalized cyclopentadienyl ligands may, in some cases, increase the reactivity but does not confer stability to air. For example, see: H. Schimanke, R. Gleiter, Organometallics 1998, 17, 275.
43. Very few complexes of the type [CpCo(CO)(alkene)] have been described: a) P. Hong, Y. Yamamoto, H. Yamazaki, J. Organo-met. Chem. 1982, 232, 71;
44. b) R. H. Hill, J. Chem. Soc. Chem. Commun. 1989, 293;
45. c) J. Okuda, K. H. Zimmermann, Chem. Ber. 1989, 122, 1645;
46. d) C. P. Lenges, M. Brookhart, J. Am. Chem. Soc. 1997, 119, 3165.
47. 8a for the cocyclization of diynes with acetone, see: D. F. Harvey, B. M. Johnson, C. S. Ung, K. P. C. Vollhardt, Synlett 1989, 15.
48. For a recent example of air-tolerant Ru-catalyzed [2+2+2] cycloaddition, see: L. Adriaenssens, L. Severa, T. Šálová, I. Císařová, R. Pohl, D. Šaman, S. V. Rocha, N. S. Finney, L. Pospíšil, P. Slavíček, F. Teply, Chem. Eur. J. 2009, 15, 1072.
49. Using dimethyl maleate instead of dimethyl fumarate resulted in a mixture of [CpCo(CO)(dimethyl fumarate)] (73% yield) and [CpCo(CO)(dimethyl maleate)] (23% yield) which could be separated by column chromatography on silica gel. The formation of the former is probably a result of photoisomerization of dimethyl maleate prior to complexation.
50. CCDC 694920 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.
51. Similar results were obtained in xylenes, hexane, and THF.
52. When 30 mg of 1a were used, 13 mg could be recovered. The collected material had undiminished catalytic activity.
53. For selected examples of [2+2+2] cycloadditions under microwave irradiation, see: a) N. Nicolaus, S. Strauss, J.-M. Neudörfl, A. Prokop, H.-G. Schmalz, Org Lett. 2009, 11, 341;
54. b) A. Mclver, D. D. Young, A. Deiters, Chem. Commun. 2008, 39, 4750;
55. c) D. D. Young, A. Deiters, Angew. Chem. 2007, 119, 5279;
56. Angew. Chem. Int. Ed. 2007, 46, 5187;
57. d) Y. Zhou, J. A. Porco, Jr., J. K. Snyder, Org. Lett. 2007, 9, 393;
58. e) R. Hrdina, A. Kadlcikova, I. Valterova, J. Hodacova, M. Kotora, Tetrahedron: Asymmetry 2006, 17, 3185.
59. Formation of benzenes by intramolecular cycloadditions of triynes have been demonstrated using microwave irradiation in the absence of catalyst, see: S. Saaby, I. R. Baxendale, S. V. Ley, Org. Biomol. Chem. 2005, 3, 3365. However, prolonged heating is often necessary (1-28 h), and, under such conditions, compound 2a did not give the benzene derivative 3a but a furan. Seemingly, at least one alkyl tether is necessary for this kind of radical cyclization. In our case, in 10 min without catalyst, no cyclization was detected.
60. Similar yields were obtained at 150°C in toluene (73%) and THF (78%). However these solvents are less convenient than DMF under microwave conditions as they require longer times to reach high temperatures.
61. 2]. For example, see: F. Montilla, T. Aviles, T. Casimiro, A. A. Ricardo, M. Nunes da Ponte, J. Organomet. Chem. 2001, 632, 113.
62. Interestingly, it was not necessary to introduce one of the reagents in large excess. For comparison, see, relative to 4b:T. Hoshi, M. Katano, E. Nozawa, T. Suzuki, H. Hagiwara, Tetrahedron Lett. 2004, 45, 3489.
63. We suspect that the mechanism involves the thermal dissociation of the fumarate ligand to give [CpCo(CO)], which might catalyze the formation of benzenes without dissociation of CO. If this were the case, no irradiation would be required and the active species could go back to fumarate once the reaction is over (hence the recovery of some catalyst). For several reasons, [CpCo(CO)] might not be the most active species for the formation of pyridines, and the photodissociation of CO might be helpful. Since CO is lost, the catalyst can not be recovered in this case, as indicated by experimental results. Density functional calculations are underway to evaluate the potential of [CpCo(CO)] as the active species in [2+2+2] cycloadditions. For mechanistic studies relevant to this discussion, see: a) N. Agenet, V. Gandon, K. P. C. Vollhardt, M. Malacria, C. Aubert, J. Am. Chem. Soc. 2007, 129, 8860;
64. b) V. Gandon, N. Agenet, K. P. C. Vollhardt, M. Malacria, C. Aubert, J. Am. Chem. Soc. 2006, 128, 8509;
65. c) G. Dazinger, M. Torres-Rodriguez, K. Kirchner, M. J. Calhorda, P. J. Costa, J. Organomet. Chem. 2006, 691, 4434.
66. E. M. Harcourt, S. R. Yonis, D. E. Lynch, D. G. Hamilton, Organometallics 2008, 27, 1653.