Chiral π-complexes of heterocycles with transition metals: A versatile new family of nucleophilic catalysts

Journal of Organic Chemistry

Volumn 61, Issue 21, 1996, Pages 7230-7231

  Ruble, J Craig ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000114544     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo961433g     Document Type: Article

References (34)

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3. (b) 4-(Dimethylamino)pyridine: Steglich, W.; Höfle, G. Angew. Chem., Int. Ed. Engl. 1969, 8, 981. See also: Litvinenko, L. M.; Kirichenko, A. I. Dokl. Akad. Nauk SSSR, Ser. Khim. 1967, 176, 97-100.
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13. Vedejs, E.; Chen, X. J. Am. Chem. Soc. 1996, 118, 1809-1810.
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16. a of azaferrocene (aqueous ethanol) = 4.5.
17. Reviews that include overviews of azaferrocene chemistry: (a) Sadimenko, A. P.; Garnovskii, A. D.; Retta, N. Coord. Chem. Rev. 1993, 126, 237-318. (b) Zakrzewski, J. Heterocycles 1990, 31, 383-396. (c) Kuhn, N. Bull. Soc. Chim. Belg. 1890, 99, 707-715.
18. Reviews that include overviews of azaferrocene chemistry: (a) Sadimenko, A. P.; Garnovskii, A. D.; Retta, N. Coord. Chem. Rev. 1993, 126, 237-318. (b) Zakrzewski, J. Heterocycles 1990, 31, 383-396. (c) Kuhn, N. Bull. Soc. Chim. Belg. 1890, 99, 707-715.
19. Reviews that include overviews of azaferrocene chemistry: (a) Sadimenko, A. P.; Garnovskii, A. D.; Retta, N. Coord. Chem. Rev. 1993, 126, 237-318. (b) Zakrzewski, J. Heterocycles 1990, 31, 383-396. (c) Kuhn, N. Bull. Soc. Chim. Belg. 1890, 99, 707-715.
20. (a) Report of N-alkylation of azaferrocene with methyl iodide: Ref. 8b.
21. (b) Report of N-acylation of 2,3,4,5-tetramethylazaferrocene with acetyl chloride: Kuhn, N.; Schulten, M.; Zauder, E.; Augart, N.; Boese, R. Chem. Ber. 1989, 122, 1891-1896.
22. We are aware of only one previous report of a pyrindinyl-metal complex: Ji, L.-N.; Kershner, D. L.; Rerek, M. E.; Basolo, F. J. Organomet. Chem. 1985, 296, 83-94.
23. 1H NMR spectra of any of the four reactions.
24. Recent reports of achiral catalysts: (a) Vedejs, E.; Diver, S. T. J. Am. Chem. Soc. 1993, 115, 3358-3359. (b) Ishihara, K.; Kubota, M.; Kurihara, H.; Yamamoto, H. J. Am. Chem. Soc. 1995, 117, 4413-4414.
25. Recent reports of achiral catalysts: (a) Vedejs, E.; Diver, S. T. J. Am. Chem. Soc. 1993, 115, 3358-3359. (b) Ishihara, K.; Kubota, M.; Kurihara, H.; Yamamoto, H. J. Am. Chem. Soc. 1995, 117, 4413-4414.
26. Recent work on catalytic asymmetric acylation: Vedejs, E.; Daugulis, O.; Diver, S. T. J. Org. Chem. 1996, 61, 430-431 and references therein.
27. Wilson, S. R.; Price, M. F. J. Org. Chem. 1984, 49, 722-725.
28. Review of nucleophile-catalyzed reactions of organosilicon compounds: Furin, G. G.; Vyazankina, O. A.; Gostevsky, B. A.; Vyazankin, N. S. Tetrahedron 1988, 44, 2675-2749.
29. Recent reviews of asymmetric cyanohydrin synthesis: (a) Effenberger, F. Angew. Chem., Int. Ed. Engl. 1994, 33, 1555-1564. (b) North, M. Synlett 1993, 807-820.
30. Recent reviews of asymmetric cyanohydrin synthesis: (a) Effenberger, F. Angew. Chem., Int. Ed. Engl. 1994, 33, 1555-1564. (b) North, M. Synlett 1993, 807-820.
31. The half-life for each of these reactions (eqs 1-3) in the presence of catalytic DMAP was less than 2 min.
32. When conducted on a 1 mmol scale in the presence of catalyst 4 (0.5-1 mol %), the three reactions afforded 89-98% isolated yields of the desired reaction products.
33. Optically active 2-methylazaferrocene has been prepared through classical resolution, but the level of enantiomeric purity was not determined: Bauer, K.; Falk, H.; Schlögl, K. Angew. Chem., Int. Ed. Engl. 1969, 8, 135.
34. For the synthesis of enantiomerically pure 2, see the supporting information.