Highly enantioselective, catalytic conjugate addition of cyanide to α,β-unsaturated imides

Journal of the American Chemical Society

Volumn 125, Issue 15, 2003, Pages 4442-4443

  Sammis, Glenn M ^a   Jacobsen, Eric N ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINO ACID; BETA AMINO ACID; CYANIDE; GAMMA AMINO ACID; IMIDE; UNCLASSIFIED DRUG;

ADDITION REACTION; ARTICLE; CATALYSIS; CATALYST; CHIRALITY; COMPLEX FORMATION; CONJUGATE; ENANTIOSELECTIVITY; SYNTHESIS;

ALKENES; AMINO ACIDS; CATALYSIS; CYANIDES; GAMMA-AMINOBUTYRIC ACID; IMIDES; STEREOISOMERISM;

EID: 0037448902     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja034635k     Document Type: Article

References (33)

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8. Best results were obtained through the use of concentrated toluene solutions. Similar enantioselectivities, but slower reaction rates, were obtained in TBME and chlorobenzene. Use of excess TMSCN (≥2.5 equiv) proved necessary for the attainment of complete conversion of the imide substrate, with improved rates and comparable enantioselectivities achieved with higher cyanide concentrations.
9. 3 solution trap. The residue was purified by flash chromatography to afford pure product 3.
10. Comparable results were obtained using ethanol or tert-butyl alcohol.
11. No reactivity was observed with imides bearing α-substitution.
12. Best results were obtained when the catalyst was dried azeotropically with toluene prior to use.
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19. Hoekstra, M. S.; Sobieray, D. M.; Schwindt, M. A.; Mulhern, T. A.; Grote, T. M.; Huckabee, B. K.; Hendrickson, V. S.; Franklin, L. C.; Granger, E. J.; Karrick, G. L. Org. Process Dev. 1997, 1, 26-38. For alternative approaches, see: (a) Brenner, M.; Seebach, D. Helv. Chim. Acta 1999, 82, 2365-2379. (b) Andruszkiewicz, R.; Siverman, R. B. Synthesis 1989. 953-955. (c) Serfass, L.; Casara, P. J. Bioorg. Med. Chem. Lett. 1998, 8, 2599-2602.
20. Hoekstra, M. S.; Sobieray, D. M.; Schwindt, M. A.; Mulhern, T. A.; Grote, T. M.; Huckabee, B. K.; Hendrickson, V. S.; Franklin, L. C.; Granger, E. J.; Karrick, G. L. Org. Process Dev. 1997, 1, 26-38. For alternative approaches, see: (a) Brenner, M.; Seebach, D. Helv. Chim. Acta 1999, 82, 2365-2379. (b) Andruszkiewicz, R.; Siverman, R. B. Synthesis 1989. 953-955. (c) Serfass, L.; Casara, P. J. Bioorg. Med. Chem. Lett. 1998, 8, 2599-2602.
21. Hoekstra, M. S.; Sobieray, D. M.; Schwindt, M. A.; Mulhern, T. A.; Grote, T. M.; Huckabee, B. K.; Hendrickson, V. S.; Franklin, L. C.; Granger, E. J.; Karrick, G. L. Org. Process Dev. 1997, 1, 26-38. For alternative approaches, see: (a) Brenner, M.; Seebach, D. Helv. Chim. Acta 1999, 82, 2365-2379. (b) Andruszkiewicz, R.; Siverman, R. B. Synthesis 1989. 953-955. (c) Serfass, L.; Casara, P. J. Bioorg. Med. Chem. Lett. 1998, 8, 2599-2602.
22. For selected examples of asymmetric catalytic approaches to 3-aryl-γ-amino acids, see: (a) Ji, J.; Barnes, D. M.; Zhang, J.; King, S. A.; Wittenberger, S. J.; Morton, H. E. J. Am. Chem. Soc. 1999, 121, 10215-10216. (b) Corey, E. J.; Zhang, F.-Y. Org. Lett. 2000, 2, 4257-4259. (c) Mazzini, C.; Lebreton, J.; Alphand, V.; Furstoss, R. J. Tetrahedron Lett. 1997, 38, 1195-1196. (d) Doyle, M. P.; Hu, W. Chirality 2002, 14, 169-172.
23. For selected examples of asymmetric catalytic approaches to 3-aryl-γ-amino acids, see: (a) Ji, J.; Barnes, D. M.; Zhang, J.; King, S. A.; Wittenberger, S. J.; Morton, H. E. J. Am. Chem. Soc. 1999, 121, 10215-10216. (b) Corey, E. J.; Zhang, F.-Y. Org. Lett. 2000, 2, 4257-4259. (c) Mazzini, C.; Lebreton, J.; Alphand, V.; Furstoss, R. J. Tetrahedron Lett. 1997, 38, 1195-1196. (d) Doyle, M. P.; Hu, W. Chirality 2002, 14, 169-172.
24. For selected examples of asymmetric catalytic approaches to 3-aryl-γ-amino acids, see: (a) Ji, J.; Barnes, D. M.; Zhang, J.; King, S. A.; Wittenberger, S. J.; Morton, H. E. J. Am. Chem. Soc. 1999, 121, 10215-10216. (b) Corey, E. J.; Zhang, F.-Y. Org. Lett. 2000, 2, 4257-4259. (c) Mazzini, C.; Lebreton, J.; Alphand, V.; Furstoss, R. J. Tetrahedron Lett. 1997, 38, 1195-1196. (d) Doyle, M. P.; Hu, W. Chirality 2002, 14, 169-172.
25. For selected examples of asymmetric catalytic approaches to 3-aryl-γ-amino acids, see: (a) Ji, J.; Barnes, D. M.; Zhang, J.; King, S. A.; Wittenberger, S. J.; Morton, H. E. J. Am. Chem. Soc. 1999, 121, 10215-10216. (b) Corey, E. J.; Zhang, F.-Y. Org. Lett. 2000, 2, 4257-4259. (c) Mazzini, C.; Lebreton, J.; Alphand, V.; Furstoss, R. J. Tetrahedron Lett. 1997, 38, 1195-1196. (d) Doyle, M. P.; Hu, W. Chirality 2002, 14, 169-172.
26. For representative alternative routes, see: Juaristi, E. Enantioselective Synthesis of β-Amino Acids; Wiley-VCH: New York, 1997. For complementary asymmetric, catalytic approaches, see: (b) Davies, H. M. L.; Venkataramani, C. Angew. Chem., Int. Ed. 2002, 41, 2197-2199. (c) Cordova, A.; Watanabe, S.; Tanaka, F.; Notz, W.; Barbas, C. F. J. Am. Chem. Soc. 2002, 124, 1866-1867.
27. For representative alternative routes, see: Juaristi, E. Enantioselective Synthesis of β-Amino Acids; Wiley-VCH: New York, 1997. For complementary asymmetric, catalytic approaches, see: (b) Davies, H. M. L.; Venkataramani, C. Angew. Chem., Int. Ed. 2002, 41, 2197-2199. (c) Cordova, A.; Watanabe, S.; Tanaka, F.; Notz, W.; Barbas, C. F. J. Am. Chem. Soc. 2002, 124, 1866-1867.
28. For representative alternative routes, see: Juaristi, E. Enantioselective Synthesis of β-Amino Acids; Wiley-VCH: New York, 1997. For complementary asymmetric, catalytic approaches, see: (b) Davies, H. M. L.; Venkataramani, C. Angew. Chem., Int. Ed. 2002, 41, 2197-2199. (c) Cordova, A.; Watanabe, S.; Tanaka, F.; Notz, W.; Barbas, C. F. J. Am. Chem. Soc. 2002, 124, 1866-1867.
29. Ninomiya, K.; Shioiri, T.; Yamada, S. Tetrahedron 1974, 30, 2151-2157.
30. Titration of a solution of (salen)Al-Cl with TMSCN led to formation of a precipitate, and TMSCI remained in solution. Direct characterization of the Al-containing product has been hampered by its low solubility.
31. This complex does not form upon treatment of 1a with HCN, consistent with the observation that the conjugate addition reaction does not take place with pregenerated HCN (vide supra). However, catalytic activity is restored if TMSCN (1 equiv relative to imide) is added.
32. Spectroscopic and kinetic data are provided as Supporting Information.
33. Closely analogous mechanisms have been revealed in epoxide ring-opening reactions catalyzed by metal salen complexes. See: Jacobsen, E. N. Acc. Chem. Res. 2000, 33, 421-431.