Dinuclear {(salen)Al} complexes display expanded scope in the conjugate cyanation of α,β-unsaturated imides

Angewandte Chemie - International Edition

Volumn 47, Issue 9, 2008, Pages 1762-1765

  Mazet, Clément ^a   Jacobsen, Eric N ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

Aluminum; Asymmetric catalysis; Cyanation; Dinuclear complexes; Kinetics

Indexed keywords

ALUMINUM; CATALYSIS; CHEMICAL REACTIONS; CHEMICAL REACTIVITY; ENANTIOSELECTIVITY;

ASYMMETRIC CATALYSIS; CYANATION; DINUCLEAR COMPLEXES; KINETICS;

AMINES;

CYANIDE; ETHYLENEDIAMINE DERIVATIVE; IMIDE; ORGANOMETALLIC COMPOUND; SALEN ALUMINUM COMPLEX; SALEN-ALUMINUM COMPLEX; TRIMETHYLSILYL CYANIDE; TRIMETHYLSILYL DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY;

CATALYSIS; CYANIDES; ETHYLENEDIAMINES; IMIDES; MOLECULAR STRUCTURE; ORGANOMETALLIC COMPOUNDS; TRIMETHYLSILYL COMPOUNDS;

EID: 41049086532     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200704461     Document Type: Article

References (20)

1. G. M. Sammis, E. N. Jacobsen, J. Am. Chem. Soc. 2003, 125, 4442-4443.
2. a) T. Mita, K. Sasaki, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 2005, 127, 514-515;
3. b) I. Fujimori, T. Mita, K. Maki, M. Shiro, A. Sato, S. Furusho, M. Kanai, M. Shibasaki, Tetrahedron 2007, 63, 5820-5831.
4. G. M. Sammis, H. Danjo, E. N. Jacobsen, J. Am. Chem. Soc. 2004, 126, 9928-9929.
5. Typically, 10-40 mol % of chiral ligand were used. Reaction time ranged from 8 h to 6 days. See ref. [2b] for details. The second generation of catalyst reported in ref. [2b] partially circumvents these limitations.
6. R. J. Konsler, J. Karl, E. N. Jacobsen, J. Am. Chem. Soc. 1998, 120, 10780-10781.
7. a) J. M. Ready, E. N. Jacobsen, J. Am. Chem. Soc. 2001, 123, 2687-2688;
8. b) J. M. Ready, E. N. Jacobsen Angew. Chem. 2002, 114, 1432-1435;
9. Angew. Chem. Int. Ed. 2002, 41, 1374-1377;
10. Angew. Chem. Int. Ed. 2002, 41, 1374-1377;
11. c) D. White, E. N. Jacobsen, Tetrahedron: Asymmetry 2003, 14, 3633-3638.
12. R. Breinbauer, E. N. Jacobsen, Angew. Chem. 2000, 112, 3750-3753;
13. Angew. Chem. Int. Ed. 2000, 39, 3604-3607.
14. a) D. A. Annis, E. N. Jacobsen, J. Am. Chem. Soc. 1999, 121, 4147-4154;
15. b) B. M. Rossbach, K. Leopold, R. Weberskirch, Angew. Chem. 2006, 118, 1331-1335;
16. Angew. Chem. Int. Ed. 2006, 45, 1309-1312.
17. See Supporting Information for a typical procedure. Data for catalysts 2a and 2b are not plotted because these catalysts were less enantioselective. After a reaction time of 20 h, catalyst 2a furnished imide 5e in 47 % yield and 86 % ee, and catalyst 2b afforded the same product in 24 % yield and 68 % ee.
18. This particular substrate requires 48 h reaction time with either the homobimetallic or the heterobimetallic systems described in references [1] and [2].
19. 1H NMR spectroscopy of the crude mixture.
20. -1. See Supporting Information for details. Similar results were obtained with catalyst 2c and 2d.