Conversion of α,β-unsaturated aldehydes into saturated esters: An umpolung reaction catalyzed by nucleophilic carbenes

Organic Letters

Volumn 7, Issue 5, 2005, Pages 905-908

  Chan, Audrey ^a   Scheidt, Karl A ^a  

^a NORTHWESTERN UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; ALDEHYDE DERIVATIVE; CARBENOID; CARBONYL DERIVATIVE; ESTER DERIVATIVE; HETEROCYCLIC COMPOUND; IMIDAZOLE DERIVATIVE;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; CHIRALITY; STRUCTURE ANALYSIS; UMPOLUNG REACTION;

EID: 15244343088     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol050100f     Document Type: Article

References (30)

1. (a) Seebach, D. Angew. Chem., Int. Ed. Engl. 1979, 18, 239-258.
2. (b) Eisch, J. J. J. Organomet. Chem. 1995, 500, 101-115.
3. (c) Pohl, M.; Lingen, B.; Muller, M. Chem. Eur. J. 2002, 8, 5289-5295.
4. Hassner, A. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 1, pp 541-577.
5. Stetter, H.; Kuhlmann, H. Org. React. 1991, 40, 407-496.
6. For a review, see: Enders, D.; Balensiefer, T. Acc. Chem. Res. 2004, 37, 534-541.
7. (a) Mattson, A. E.; Bharadwaj, A. R.; Scheidt, K. A. J. Am. Chem. Soc. 2004, 126, 2314-2315.
8. (b) Mattson, A. E.; Scheidt, K. A. Org. Lett. 2004, 6, 4363-4366.
9. (c) A. E.; Bharadwaj, A. R.; Scheidt, K. A. Org. Lett. 2004, 6, 2465-2468.
10. (d) Clark, C. T.; Lake, J. F.; Scheidt, K. A. J. Am. Chem. Soc. 2004, 126, 84-85.
11. (a) List, B. Synlett 2001, 1675-1686.
12. (b) Dalko, P. I.; Moisan, L. Angew. Chem., Int. Ed. 2004, 43, 5138-5175 and references therein.
13. For reviews on homoenolate equivalents, see: (a) Hoppe, D.; Kraemer, T.; Schwark, J.; Zschage, O. Pure Appl. Chem. 1990, 62, 1999-2006. (b) Ahlbrecht, H.; Beyer, U. Synthesis 1999, 365-390.
14. For reviews on homoenolate equivalents, see: (a) Hoppe, D.; Kraemer, T.; Schwark, J.; Zschage, O. Pure Appl. Chem. 1990, 62, 1999-2006. (b) Ahlbrecht, H.; Beyer, U. Synthesis 1999, 365-390.
15. For recent examples, see: Seppi, M.; Kalkofen, R.; Reupohl, J.; Frohlich, R.; Hoppe, D. Angew. Chem., Int. Ed. 2004, 43, 1423-1427. (c) Reuber, J.; Frohlich, R.; Hoppe, D. Org. Lett. 2004, 6, 783-786. (d) Hilgenkamp, R.; Zercher, C. K. Org. Lett. 2001, 3, 3037-3040. (e) Whisler, M. C.; Beak, P. J. Org. Chem. 2002, 68, 1207-1215.
16. For recent examples, see: Seppi, M.; Kalkofen, R.; Reupohl, J.; Frohlich, R.; Hoppe, D. Angew. Chem., Int. Ed. 2004, 43, 1423-1427. (c) Reuber, J.; Frohlich, R.; Hoppe, D. Org. Lett. 2004, 6, 783-786. (d) Hilgenkamp, R.; Zercher, C. K. Org. Lett. 2001, 3, 3037-3040. (e) Whisler, M. C.; Beak, P. J. Org. Chem. 2002, 68, 1207-1215.
17. For recent examples, see: Seppi, M.; Kalkofen, R.; Reupohl, J.; Frohlich, R.; Hoppe, D. Angew. Chem., Int. Ed. 2004, 43, 1423-1427. (c) Reuber, J.; Frohlich, R.; Hoppe, D. Org. Lett. 2004, 6, 783-786. (d) Hilgenkamp, R.; Zercher, C. K. Org. Lett. 2001, 3, 3037-3040. (e) Whisler, M. C.; Beak, P. J. Org. Chem. 2002, 68, 1207-1215.
18. For recent examples, see: Seppi, M.; Kalkofen, R.; Reupohl, J.; Frohlich, R.; Hoppe, D. Angew. Chem., Int. Ed. 2004, 43, 1423-1427. (c) Reuber, J.; Frohlich, R.; Hoppe, D. Org. Lett. 2004, 6, 783-786. (d) Hilgenkamp, R.; Zercher, C. K. Org. Lett. 2001, 3, 3037-3040. (e) Whisler, M. C.; Beak, P. J. Org. Chem. 2002, 68, 1207-1215.
19. (a) Breslow, R.; Schmuck, C. Tetrahedron Lett. 1996, 37, 8241-8242.
20. (b) White, M. J.; Leeper, F. J. J. Org. Chem. 2001, 66, 5124-5131.
21. (a) Bourissou, D.; Guerret, O.; Gabbai, F. P.; Bertrand, G. Chem. Rev. 2000, 100, 39-91.
22. (b) Herrmann, W. A. Angew. Chem., Int. Ed. 2002, 41, 1291-1309.
23. Similar activated esters have been implicated in the reactions between N-heterocyclic carbenes and α-halo aldehydes (Reynolds, N. T.; de Alaniz, J. R.; Rovis, T. J. Am. Chem. Soc. 2004, 126, 9518-9519) or epoxy-aldehydes (Chow, K. Y. K.; Bode, J. W. J. Am. Chem. Soc. 2004, 126, 8126-8127).
24. Similar activated esters have been implicated in the reactions between N-heterocyclic carbenes and α-halo aldehydes (Reynolds, N. T.; de Alaniz, J. R.; Rovis, T. J. Am. Chem. Soc. 2004, 126, 9518-9519) or epoxy-aldehydes (Chow, K. Y. K.; Bode, J. W. J. Am. Chem. Soc. 2004, 126, 8126-8127).
25. For recent and related approaches accessing homoenolates from α,β-unsaturated aldehydes for the synthesis of γ- butyrolactones, see: (a) Sohn, S. S.; Rosen, J. W.; Bode, J. J. Am. Chem. Soc. 2004, 126, 14370-14371. (b) Glorius, F., Burstein, C. Angew. Chem., Int. Ed. 2004, 43, 6205-6208.
26. For recent and related approaches accessing homoenolates from α,β-unsaturated aldehydes for the synthesis of γ- butyrolactones, see: (a) Sohn, S. S.; Rosen, J. W.; Bode, J. J. Am. Chem. Soc. 2004, 126, 14370-14371. (b) Glorius, F., Burstein, C. Angew. Chem., Int. Ed. 2004, 43, 6205-6208.
27. For the synthesis of D, see: (a) Rivas, F. M.; Giessert, A. J.; Diver, S. T. J. Org. Chem. 2002, 67, 1708-1711. (b) Rivas, F. M.; Riaz, U.; Giessert, A.; Smulik, J. A.; Diver, S. T. Org. Lett. 2001, 3, 2673-2676.
28. For the synthesis of D, see: (a) Rivas, F. M.; Giessert, A. J.; Diver, S. T. J. Org. Chem. 2002, 67, 1708-1711. (b) Rivas, F. M.; Riaz, U.; Giessert, A.; Smulik, J. A.; Diver, S. T. Org. Lett. 2001, 3, 2673-2676.
29. For information on selectivity factors (s) in kinetic resolutions, see: (a) Kagan, H. B.; Fiaud, J. C. In Topics in Stereochemistry; Eliel, E. L., Ed.; Wiley: New York, 1988; Vol. 18, pp 249-330. (b) Chen, C. S.; Fujimoto, Y.; Girdaukas, G.; Sih, C. J. J. Am. Chem. Soc. 1982, 104, 7294-7299. See Supporting Information for details.
30. For information on selectivity factors (s) in kinetic resolutions, see: (a) Kagan, H. B.; Fiaud, J. C. In Topics in Stereochemistry; Eliel, E. L., Ed.; Wiley: New York, 1988; Vol. 18, pp 249-330. (b) Chen, C. S.; Fujimoto, Y.; Girdaukas, G.; Sih, C. J. J. Am. Chem. Soc. 1982, 104, 7294-7299. See Supporting Information for details.