Cooperative catalysis of a cationic ruthenium complex, amine base, and Na salt: Catalytic activation of acetonitrile as a nucleophile

Journal of the American Chemical Society

Volumn 126, Issue 42, 2004, Pages 13632-13633

  Kumagai, Naoya ^a   Matsunaga, Shigeki ^a   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ACETONITRILE DERIVATIVE; AMINE; RUTHENIUM COMPLEX; SODIUM;

ADDITION REACTION; ARTICLE; CATALYSIS; CHEMICAL REACTION; ELECTRON TRANSPORT; MOLECULAR DYNAMICS; MOLECULAR INTERACTION; REACTION ANALYSIS; SUBSTITUTION REACTION;

EID: 6444227416     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0450509     Document Type: Article

References (32)

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17. Although there are substantial reports on Lewis acidic activation of simple alkylnitriles as electrophiles (reviews: (a) Kukushkin, V. Y.; Pombeiro, A. J. L. Chem. Rev. 2002, 102, 1771. (b) Michelin, R. A.; Mozzon, M.; Bertani, R. Coord. Chem. Rev. 1996, 147, 299.), activation as nucleophiles is rare (stoichiometric reaction: (c) English. A. D.; Herskovitz, T. J. Am. Chem. Soc. 1977, 99, 1648. (d) Ittel, S. D.; Tolman, C. A.; English, A. D.; Jesson, J. P. J. Am. Chem. Soc. 1978, 100, 7577.
18. Although there are substantial reports on Lewis acidic activation of simple alkylnitriles as electrophiles (reviews: (a) Kukushkin, V. Y.; Pombeiro, A. J. L. Chem. Rev. 2002, 102, 1771. (b) Michelin, R. A.; Mozzon, M.; Bertani, R. Coord. Chem. Rev. 1996, 147, 299.), activation as nucleophiles is rare (stoichiometric reaction: (c) English. A. D.; Herskovitz, T. J. Am. Chem. Soc. 1977, 99, 1648. (d) Ittel, S. D.; Tolman, C. A.; English, A. D.; Jesson, J. P. J. Am. Chem. Soc. 1978, 100, 7577.
19. Although there are substantial reports on Lewis acidic activation of simple alkylnitriles as electrophiles (reviews: (a) Kukushkin, V. Y.; Pombeiro, A. J. L. Chem. Rev. 2002, 102, 1771. (b) Michelin, R. A.; Mozzon, M.; Bertani, R. Coord. Chem. Rev. 1996, 147, 299.), activation as nucleophiles is rare (stoichiometric reaction: (c) English. A. D.; Herskovitz, T. J. Am. Chem. Soc. 1977, 99, 1648. (d) Ittel, S. D.; Tolman, C. A.; English, A. D.; Jesson, J. P. J. Am. Chem. Soc. 1978, 100, 7577.
20. Although there are substantial reports on Lewis acidic activation of simple alkylnitriles as electrophiles (reviews: (a) Kukushkin, V. Y.; Pombeiro, A. J. L. Chem. Rev. 2002, 102, 1771. (b) Michelin, R. A.; Mozzon, M.; Bertani, R. Coord. Chem. Rev. 1996, 147, 299.), activation as nucleophiles is rare (stoichiometric reaction: (c) English. A. D.; Herskovitz, T. J. Am. Chem. Soc. 1977, 99, 1648. (d) Ittel, S. D.; Tolman, C. A.; English, A. D.; Jesson, J. P. J. Am. Chem. Soc. 1978, 100, 7577.
21. For an example of Lewis acid-amine (more than a stoichiometric amount) cooperative deprotonation of acetonitrile: Sugasawa, T.; Toyoda, T. Synth. Commun. 1979, 9, 553.
22. Reviews: (a) Trost, B. M.; Toste, F. D.; Pinkerton, A. B. Chem. Rev. 2001, 101, 2067. (b) Slugovc, C.; Rüba, E.; Schmid, R.; Kirchner, K.; Mereiter, K. Monatsh. Chem. 2000, 131, 1241. An excellent example of Ru-catalyzed in situ activation of malonate as a nucleophile: (c) Watanabe, M.; Murata, K.; Ikariya, T. J. Am. Chem. Soc. 2003, 125, 7508.
23. Reviews: (a) Trost, B. M.; Toste, F. D.; Pinkerton, A. B. Chem. Rev. 2001, 101, 2067. (b) Slugovc, C.; Rüba, E.; Schmid, R.; Kirchner, K.; Mereiter, K. Monatsh. Chem. 2000, 131, 1241. An excellent example of Ru-catalyzed in situ activation of malonate as a nucleophile: (c) Watanabe, M.; Murata, K.; Ikariya, T. J. Am. Chem. Soc. 2003, 125, 7508.
24. Reviews: (a) Trost, B. M.; Toste, F. D.; Pinkerton, A. B. Chem. Rev. 2001, 101, 2067. (b) Slugovc, C.; Rüba, E.; Schmid, R.; Kirchner, K.; Mereiter, K. Monatsh. Chem. 2000, 131, 1241. An excellent example of Ru-catalyzed in situ activation of malonate as a nucleophile: (c) Watanabe, M.; Murata, K.; Ikariya, T. J. Am. Chem. Soc. 2003, 125, 7508.
25. All three catalytic components are commercially available.
26. Conditions are supposed to be as mild as Masamune-Roush conditions for HWE reaction. Blanchette, M. A.; Choy, W.; Davis, J. T.; Essenfeld, A. P.; Masamune, S.; Roush, W. R.; Sakai, T. Tetrahedron Lett. 1984, 25, 2183.
27. See Supporting Information for details.
28. 13C δ 1.97 ppm).
29. Fleming, F. F.; Shook B. C. Tetrahedron 2002, 58, 1.
30. Rate dependencies of reaction on DBU, 3, and 1a were 1.0, 0.64, and 0 order, respectively. See Supporting Information for details.
31. Dissociative pathway has been suggested for the ligand exchange of CpRu complex. Therefore, the formation of 8 would be easier from 7 than that from 3 in which dissociation of acetonitrile is required. Luginbühl, W.; Zbinden, P.; Pittet, P. A.; Armbruster, T.; Bürgi, H.-B.; Merbach, A. E.; Ludi, A. Inorg. Chem. 1991, 30, 2355.
32. 6 had no beneficial effect on reaction rate and catalyst turnover.