Enantioselective addition of phenyl and alkyl acetylenes to imines catalyzed by chiral Cu(I) complexes

Tetrahedron Letters

Volumn 45, Issue 47, 2004, Pages 8705-8708

  Benaglia, Maurizio ^a   Negri, Diego ^a   Dell'Anna, Gianmaria ^a  

^a UNIVERSITY OF MILAN   (Italy)

Author keywords

Acetylenes addition; Asymmetric catalysis; Chiral bis imines; Chiral ligands; Propargyl amines

Indexed keywords

ACETYLENE DERIVATIVE; COPPER COMPLEX; IMINE;

ADDITION REACTION; ARTICLE; CATALYSIS; CHEMICAL REACTION; CHIRALITY; ENANTIOSELECTIVITY; ROOM TEMPERATURE; SYNTHESIS;

EID: 7044272565     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2004.09.138     Document Type: Article

References (29)

1. Review: E.N. Jacobsen A. Pfaltz H. Yamamoto Comprehensive Asymmetric Catalysis Vols. I-III 1999 Springer Berlin
2. For a review of asymmetric synthesis of propargylamines, see: J. Blanchet, M. Bonin, and L. Micouin Org. Prep. Proced. Int. 34 2002 459
3. Reviews: L. Pu, and H.B. Yu Chem. Rev. 101 2001 757
4. D.E. Frantz, R. Fassler, C.S. Tomooka, and E.M. Carreira Acc. Chem. Res. 33 2000 373
5. For addition of organometallic reagents to chiral imines see: R. Bloch Chem. Rev. 98 1998 1407
6. D. Enders, and U. Reinhold Tetrahedron: Asymmetry 8 1997 1895 See also
7. M.A. Huffman, N. Yasuda, A.E. DeCamp, and E.J.J. Grabowski J. Org. Chem. 60 1995 1590
8. D.E. Frantz, R. Fassler, J. Oetiker, and E.M. Carreira Angew. Chem., Int. Ed. 41 2002 3054
9. D.E. Frantz, R. Fassler, and E.M. Carreira J. Am. Chem. Soc. 121 1999 11245 and references cited therein
10. For a few selected examples of interesting methodologies affording racemic compounds see also: C. Fischer, and E.M. Carreira Org. Lett. 3 2001 4319
11. C. Fischer, and E.M. Carreira Org. Lett. 6 2004 1497
12. C. Wei, Z. Li, and C. Li J. Org. Lett. 5 2003 4473
13. C. Koradin, K. Polborn, and P. Knochel Angew. Chem., Int. Ed. 41 2002 2535
14. N. Gommermann, C. Koradin, K. Polborn, and P. Knochel Angew. Chem., Int. Ed. 42 2003 5763
15. J.F. Traverse, A.H. Hoveyda, and M.L. Snapper Org. Lett. 5 2003 3273 See also
16. L.C. Akullian, A.H. Hoveyda, and M.L. Snapper Angew. Chem., Int. Ed. 42 2003 4244
17. C. Wie, and C.J. Li J. Am. Chem. Soc. 124 2002 5638
18. A. Puglisi, M. Benaglia, R. Annunziata, and A. Bologna Tetrahedron Lett. 44 2003 2947
19. H. Suga, A. Kakehi, S. Ito, T. Ibata, T. Fudo, Y. Watanabe, and Y. Kinoshita Bull. Chem. Soc. Jpn. 76 2003 189
20. C.J. Sanders, K.M. Gillespie, D. Bell, and P. Scott J. Am. Chem. Soc. 122 2000 7132
21. C.J. Sanders, K.M. Gillespie, and P. Scott Tetrahedron: Asymmetry 12 2001 1055
22. Binaphthyl diamine is available in both enantiomeric forms and it costs about three times less than pyridyl-bis-oxazolines employed by Li and 20 times less than Quinap used by Knochel. Products 1, 2, 3, 4, 5 were obtained in 98%, 85% 91%, 98%, 77% yields, respectively
23. F. Vogtle, R. Thomessen, E. Steckhan, and K. Schumacher Tetrahedron Lett. 26 1985 2077 Product 6 was obtained in 97% yield
24. M.T. Reetz, G. Haderlein, and K. Angermund J. Am. Chem. Soc. 122 2000 996 Following the reported procedure, in our hands, product 7 was obtained in 51% yield after chromatographic purification
25. At the end of reaction, after filtration onto a Celite cake, the recovered crude reaction mixture did not show any trace of phenyl acetylene addition to the chiral bis-imine ligand, but only product 9 and eventually non reacted starting material 8
26. R of the minor enantiomer: 16.1 min
27. Addition did not occur in methanol, N,N-dimethyl-formammide and 9/1 mixture of toluene/water
28. See also: C.J. Li, and C. Wei Chem. Commun. 2002 268
29. To our knowledge this is the first example of direct, enantioselective catalytic addition to imines of alkyl acetylenes; for other examples of use of alkyl acetylenes in other methodologies see Refs. 6 and 7