Carboamination: Additions of imine C=N bonds across alkynes catalyzed by imidozirconium complexes

Angewandte Chemie - International Edition

Volumn 43, Issue 40, 2004, Pages 5372-5374

  Ruck, Rebecca T ^a   Zuckerman, Rebecca L ^b   Krska, Shane W ^c   Bergman, Robert G ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b PLEXXIKON INC   (United States)

^c MERCK RESEARCH LABORATORIES   (United States)

Author keywords

Alkynes; Carboamination; Imines; Zirconium

Indexed keywords

CATALYSIS; CHEMICAL BONDS; HYDROCARBONS; SUBSTITUTION REACTIONS;

ALKYNES; CARBOAMINATION;

AMINATION;

ALKYNE DERIVATIVE; BENZENE DERIVATIVE; CARBON; IMIDOZIRCONIUM COMPLEX; IMINE; NITROGEN; SOLVENT; UNCLASSIFIED DRUG; ZIRCONIUM DERIVATIVE;

ADDITION REACTION; AMINATION; ARTICLE; CARBOAMINATION; CATALYSIS; CATALYST; CHEMICAL BOND; CHEMICAL MODIFICATION; CHEMICAL REACTION; CONCENTRATION RESPONSE; CYCLOADDITION; DIMERIZATION; DISSOCIATION; REACTION ANALYSIS; REPRODUCIBILITY; STEREOCHEMISTRY; SUBSTITUTION REACTION; SYNTHESIS; TECHNIQUE; TEMPERATURE DEPENDENCE;

ALKYNES; AMINATION; CATALYSIS; IMINES; MODELS, CHEMICAL; ORGANOMETALLIC COMPOUNDS; STEREOISOMERISM; ZIRCONIUM;

EID: 7244247118     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200461063     Document Type: Article

References (27)

1. a) P. J. Walsh, R. G. Bergman, J. Am. Chem. Soc. 1992, 114, 1708;
2. b) A. M. Baranger, P. J. Walsh, R. G. Bergman, J. Am. Chem. Soc. 1993, 115, 2753.
3. Imidotitanium-catalyzed hydroamination reactions are also known: a) L. Ackermann, R. N. Loy, R. G. Bergman, J. Am. Chem. Soc. 2003, 125, 11956;
4. b) J. S. Johnson, R. G. Bergman, J. Am. Chem. Soc. 2001, 123, 2923;
5. c) Y. Shi, J. T. Ciszewski, A. L. Odom, Organometallics 2001, 20, 3967;
6. d) E. Haak, I. Bytschkov, S. Doye, Angew. Chem. 1999, 111, 3584; Angew. Chem. Int. Ed. 1999, 38, 3389.
7. d) E. Haak, I. Bytschkov, S. Doye, Angew. Chem. 1999, 111, 3584; Angew. Chem. Int. Ed. 1999, 38, 3389.
8. T. A. Hanna, A. M. Baranger, R. G. Bergman, J. Org. Chem. 1995, 60, 4532.
9. R. T. Ruck, R. G. Bergman, Organometallics 2004, 23, 2231.
10. P. J. Walsh, R. G. Bergman, Organometallics 1993, 12, 3705.
11. Odom and co-workers have developed a titanium-catalyzed three-component coupling of amines, alkynes, and isonitriles to afford α,β- unsaturated β-iminoamines: C. Cao, Y. Shi, A. L. Odom, J. Am. Chem. Soc. 2003, 125, 2880.
12. Kobayashi and co-workers have reported a Lewis acid-catalyzed reaction between imines and alkynyl sulfides to generate α,β-unsaturated thioimidates. This reaction appears to proceed by [2+2] cycloaddition followed by retro-[2+2] cycloaddition to afford the observed products: H. Ishitani, S. Nagayama, S. Kobayashi, J. Org. Chem. 1996, 61, 1902.
13. Qian and Ma have reported a reaction analogous to that described in reference [7] with alkynyl selenides as substrates: Y. Ma, C. Qian, Tetrahedron Lett. 2000, 41, 945.
14. Coupling reactions between alkynes and oxyalkynes have been reported to yield α,β-unsaturated carbonyl compounds: a) M. Curini, F. Epitano, F. Maltese, O. Rosati, Synlett 2003, 552;
15. b) M. Shindo, S. Oya, R. Murakami, Y. Sato, K. Shishido, Tetrahedron Lett. 2000, 41, 5947;
16. c) M. Shindo, S. Oya, Y. Sato, K. Shishido, Heterocycles 2000, 52, 1143.
17. P. J. Walsh, F. J. Hollander, R. G. Bergman, J. Am. Chem. Soc. 1988, 110, 8729.
18. See ref. [4]. This observation implicates an alternative effect, speculatively pre-coordination of the electron-withdrawing group oxygen atom to zirconium, in the previously reported chemistry.
19. The product of this reaction has been designated 17g to maximize consistency between starting imine and product numbering.
20. Attempts to insert imines into the analogous bis(p-bromophenyl)acetylene were unsuccessful.
21. For more information on potential suitable alkynes, see: S. Y. Lee, R. G. Bergman, Tetrahedron 1995, 51, 4255.
22. This reaction proceeds via p-methoxyphenylimidozirconocene complex 13b.
23. a) L. E. Overman, C. E. Owen, M. M. Pavan, C. J. Richards, Org. Lett. 2003, 5, 1809;
24. b) D. R. Kronenthal, C. Y. Han, M. K. Taylor, J. Org. Chem. 1982, 47, 2765.
25. Efforts to generate imidozirconium compound 13a in situ from an analogous precursor led to multiple decomposition products.
26. R. T. Ruck, R. G. Bergman, Angew. Chem. 2004, 116; Angew. Chem. Int. Ed. 2004, 43.
27. R. T. Ruck, R. G. Bergman, Angew. Chem. 2004, 116; Angew. Chem. Int. Ed. 2004, 43.