Selectivity in nickel-catalyzed rearrangements of cyclopropylen-ynes

Journal of the American Chemical Society

Volumn 127, Issue 16, 2005, Pages 5798-5799

  Zuo, Gang ^a   Louie, Janis ^a  

^a UNIVERSITY OF UTAH   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

[3 (2 BUTYNYLOXY) 1 PROPENYL]CYCLOPROPANE; CYCLOHEPTANE DERIVATIVE; CYCLOPENTANE; CYCLOPROPANE DERIVATIVE; NICKEL; TRANSITION ELEMENT; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; ISOMERIZATION; REACTION ANALYSIS; ROOM TEMPERATURE; SUBSTITUTION REACTION;

EID: 17744370539     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja043253r     Document Type: Article

References (26)

1. (a) Nakamura, I.; Yamamoto, Y. Chem. Rev. 2004, 104, 2127.
2. (b) López, F.; Delgado, A.; Rodríguez, J. R.; Castedo, L.; Mascareñas, J. L. J. Am. Chem. Soc. 2004, 126, 10262.
3. (c) Cadran, N.; Cariou, K.; Hervé, G.; Aubert, C.; Fensterbank, L.; Malacria, M.; Marco-Contelles, J. J. Am. Chem. Soc. 2004, 126, 3408.
4. (d) Ni, Y.; Montgomery, J. J. Am. Chem. Soc. 2004, 126, 11162.
5. (e) Aubert, C.; Buisine, O.; Malacria, M. Chem. Rev. 2002, 102, 813.
6. (f) Trost, B. M.; Toste, F. D.; Pinkerton, A. B. Chem. Rev. 2001, 101, 2067.
7. (g) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49.
8. (a) Zuo, G.; Louie, J. Angew. Chem., Int. Ed. 2004, 43, 2277.
9. In contrast, the Ir-catalyzed cyclization of cyclopropylen-ynes provides 1,3-dienes with the cyclopropyl ring intact. See: (b) Chatani, N.; Inoue, H.; Morimoto, T.; Muto, T.; Murai, S. J. Org. Chem. 2001, 66, 4433.
10. For Rh, see: (a) Wender, P. A.; Barzilay, C. M.; Dyckman, A. J. J. Am. Chem. Soc. 2001, 125, 179. (b) Wender, P. A.; Sperandio, D. A. J. Org. Chem. 1998, 63, 4164. (c) Binger, P.; Wedermeann, P.; Kozhushkov, S. I.; de Meijere, A. Eur. J. Org. Chem. 1998, 113, 3. (d) Wender, P. A.; Takahashi, H.; Witulski, B. J. Am. Chem. Soc. 1995, 117, 4720. For Ru, see: (e) Trost, B. M.; Toste, F. D.; Shen, H. J. Am. Chem. Soc. 2000, 122, 2379.
11. For Rh, see: (a) Wender, P. A.; Barzilay, C. M.; Dyckman, A. J. J. Am. Chem. Soc. 2001, 125, 179. (b) Wender, P. A.; Sperandio, D. A. J. Org. Chem. 1998, 63, 4164. (c) Binger, P.; Wedermeann, P.; Kozhushkov, S. I.; de Meijere, A. Eur. J. Org. Chem. 1998, 113, 3. (d) Wender, P. A.; Takahashi, H.; Witulski, B. J. Am. Chem. Soc. 1995, 117, 4720. For Ru, see: (e) Trost, B. M.; Toste, F. D.; Shen, H. J. Am. Chem. Soc. 2000, 122, 2379.
12. For Rh, see: (a) Wender, P. A.; Barzilay, C. M.; Dyckman, A. J. J. Am. Chem. Soc. 2001, 125, 179. (b) Wender, P. A.; Sperandio, D. A. J. Org. Chem. 1998, 63, 4164. (c) Binger, P.; Wedermeann, P.; Kozhushkov, S. I.; de Meijere, A. Eur. J. Org. Chem. 1998, 113, 3. (d) Wender, P. A.; Takahashi, H.; Witulski, B. J. Am. Chem. Soc. 1995, 117, 4720. For Ru, see: (e) Trost, B. M.; Toste, F. D.; Shen, H. J. Am. Chem. Soc. 2000, 122, 2379.
13. For Rh, see: (a) Wender, P. A.; Barzilay, C. M.; Dyckman, A. J. J. Am. Chem. Soc. 2001, 125, 179. (b) Wender, P. A.; Sperandio, D. A. J. Org. Chem. 1998, 63, 4164. (c) Binger, P.; Wedermeann, P.; Kozhushkov, S. I.; de Meijere, A. Eur. J. Org. Chem. 1998, 113, 3. (d) Wender, P. A.; Takahashi, H.; Witulski, B. J. Am. Chem. Soc. 1995, 117, 4720. For Ru, see: (e) Trost, B. M.; Toste, F. D.; Shen, H. J. Am. Chem. Soc. 2000, 122, 2379.
14. For Rh, see: (a) Wender, P. A.; Barzilay, C. M.; Dyckman, A. J. J. Am. Chem. Soc. 2001, 125, 179. (b) Wender, P. A.; Sperandio, D. A. J. Org. Chem. 1998, 63, 4164. (c) Binger, P.; Wedermeann, P.; Kozhushkov, S. I.; de Meijere, A. Eur. J. Org. Chem. 1998, 113, 3. (d) Wender, P. A.; Takahashi, H.; Witulski, B. J. Am. Chem. Soc. 1995, 117, 4720. For Ru, see: (e) Trost, B. M.; Toste, F. D.; Shen, H. J. Am. Chem. Soc. 2000, 122, 2379.
15. For leading reviews on NHCs, see: (a) Arduengo, A. J., III. Acc. Chem. Res. 1999, 32, 913. (b) Herrmann, W. A. Angew. Chem., Int. Ed. 2002, 41, 1290. (c) Bourissou, D.; Guerret, O.; Gabbaï, F. P.; Bertrand, G. Chem. Rev. 2000, 100, 39. [ICy = 1,3-dicyclohexylimidazol-2-ylidene; IAd = 1,3-diadamantylimidazol-2-ylidene; ItBu = 1,3-di-tert-butylimidazol-2-ylidene; IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; SIPr = 1,3-bis(2,6- diisopropylphenyl)-4,5-dihydroimidazolin-2-ylidene.]
16. For leading reviews on NHCs, see: (a) Arduengo, A. J., III. Acc. Chem. Res. 1999, 32, 913. (b) Herrmann, W. A. Angew. Chem., Int. Ed. 2002, 41, 1290. (c) Bourissou, D.; Guerret, O.; Gabbaï, F. P.; Bertrand, G. Chem. Rev. 2000, 100, 39. [ICy = 1,3-dicyclohexylimidazol-2-ylidene; IAd = 1,3-diadamantylimidazol-2-ylidene; ItBu = 1,3-di-tert-butylimidazol-2-ylidene; IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; SIPr = 1,3-bis(2,6- diisopropylphenyl)-4,5-dihydroimidazolin-2-ylidene.]
17. For leading reviews on NHCs, see: (a) Arduengo, A. J., III. Acc. Chem. Res. 1999, 32, 913. (b) Herrmann, W. A. Angew. Chem., Int. Ed. 2002, 41, 1290. (c) Bourissou, D.; Guerret, O.; Gabbaï, F. P.; Bertrand, G. Chem. Rev. 2000, 100, 39. [ICy = 1,3-dicyclohexylimidazol-2-ylidene; IAd = 1,3-diadamantylimidazol-2-ylidene; ItBu = 1,3-di-tert-butylimidazol-2-ylidene; IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; SIPr = 1,3-bis(2,6- diisopropylphenyl)-4,5-dihydroimidazolin-2-ylidene.]
18. Pinke, P. A.; Stauffer, R. D.; Miller, R. G. J. Am. Chem. Soc. 1974, 96, 4229.
19. Rearrangements proceeded smoothly in the presence of a variety of radical traps (e.g., 2,6-di-tert-butyl-4-methylphenol, 1,4-cyclohexadiene, phenyl disulfide, glavinoxyl).
20. It is unclear at this time whether 6 would result from 5a or 5b. A variety of Ni compounds are known to catalyze cycloaddition reactions of enynes via initial oxidative coupling between an alkene and alkyne (see ref 8). Thus, a similar pathway could led to the formation of 6 via intermediate 5a. Indeed, a similar mechanism has been proposed for analogous Rh-and Ru-catalyzed chemistry (see ref 3). However, we recently discovered that the Ni/NHC catalyst system mediates the isomerization of VCPs. Consequently, 6 may be derived from the initial isomerization of the VCP (5b) and subsequent insertion of the alkyne (see ref 2a).
21. (a) Zhang, M.; Buchwald, S. L. J. Org. Chem. 1996, 61, 4498.
22. (b) Wender, P. A.; Smith, T. E. J. Org. Chem. 1995, 60, 2962.
23. Tamao, K.; Kobayashi, K.; Ito, Y. J. Am. Chem. Soc. 1988, 110, 1286.
24. 4 (10 mol %) to Ni/ItBu-catalyzed reactions of 1d led to complete conversion and formation of 4d. We are currently investigating the isomerization mechanism.
25. Dorta, R.; Stevens, E. D.; Scott, N. M.; Costabile, C.; Cavallo, L.; Hoff, C. D.; Nolan, S. P. J. Am. Chem. Soc. 2005, 127, 2485.
26. When Ni/SIPr was used as the catalyst, further isomerization occurred to give a mixture of products. As shown in Table 1, Ni/ItBu is a less active catalyst system than Ni/SIPr, which allows for the selective formation of 19.