Catalytic direct asymmetric Michael reactions: Taming naked aldehyde donors

Organic Letters

Volumn 3, Issue 23, 2001, Pages 3737-3740

  Betancort, Juan M ^a   Barbas III, Carlos F ^a  

^a SCRIPPS RESEARCH INSTITUTE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

2 (MORPHOLINOMETHYL)PYRROLIDINE; 2-(MORPHOLINOMETHYL)PYRROLIDINE; ALDEHYDE; ALKENE; DYES, REAGENTS, INDICATORS, MARKERS AND BUFFERS; MORPHOLINE DERIVATIVE; PYRROLE DERIVATIVE; PYRROLIDINE DERIVATIVE;

ARTICLE; CATALYSIS; CHEMISTRY; KINETICS; STEREOISOMERISM; SYNTHESIS; TEMPERATURE;

ALDEHYDES; ALKENES; CATALYSIS; INDICATORS AND REAGENTS; KINETICS; MORPHOLINES; PYRROLES; PYRROLIDINES; STEREOISOMERISM; TEMPERATURE;

EID: 0035891780     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0167006     Document Type: Article

References (56)

1. Perlmutter, P. Conjugate Addition Reactions in Organic Synthesis: Pergamon Press: Oxford. 1992.
2. For general reviews on the asymmetric Michael reaction, see: (a) Krause, N,; Hoffmann-Roder, A. Synthesis 2001, 171-196.
3. (b) Sibi, M. P.; Manyem, S. Tetrahedron 2000, 56, 8033-8061.
4. (c) Tomioka, K.; Nagaoka, Y. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin. 1999; Vol. III. pp 1105-1120.
5. (d) Yamaguchi, M. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.: Springer: Berlin, 1999; Vol. III, pp 1121-1139.
6. (e) Leonard, J.; Diez-Barra, E.; Merino, S. Eur. J. Org. Chem. 1998, 10, 2051-2061.
7. (a) Chataigner, I.; Gennari, C.; Ongeri, S.; Piarulli, U.; Ceccarelli, S. Chem. Eur. J. 2001, 7, 2628-2634.
8. (b) Alexakis, A.; Benhaim, C. Tetrahedron: Asymmetry 2001, 12, 1151-1157.
9. (c) Evans, D. A.; Rovis, T.; Kozlowski, M. C.; Downey, C. W.; Tedrow, J. S. J. Am. Chem. Soc. 2000, 122, 9134-9142.
10. (d) Kim, Y. S.; Matsunaga, S.; Das, J.; Sekine, A.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 6506-6507.
11. (e) Arnold, L. A.; Imbos, R.; Mandoli, A.; de Vries, A. H. M.; Naasz, R.; Feringa, B. L. Tetrahedron 2000, 56, 2865-2878.
12. (f) Ji, J.; Barnes, D. M.; Zhang, J.; King, S. A.; Wittenberger, S. J.; Morton, H. E. J. Am. Chem. Soc. 1999, 121, 10215-10216.
13. (g) Kitajima, H.; Katsuki, T. Synlett 1997, 568-570.
14. (h) Arai, T.; Sasai, H.; Aoe, K.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1996, 35, 104-106.
15. (i) Yamaguchi, M.; Shiraishi, T.; Hirama, M. J. Org. Chem. 1996, 61, 3520-3530.
16. (a) Paras, N. A.; MacMillan, D. W. C. J. Am. Chem. Soc. 2001, 123, 4370-4371.
17. (b) Hanessian, S.; Pham, V. Org. Lett. 2000, 2, 2975-2978.
18. (c) Perrard, T.; Plaquevent, J.-C.; Desmurs, J.-R.: Hebrault, D. Org. Lett. 2000, 2, 2959-2962.
19. (d) Corey, E. J.; Zhang, F.-Y. Org. Lett. 2000, 2, 1097-1100.
20. (a) Yasuda, K.; Shindo, M.; Koga, K. Tetrahedron Lett. 1996, 37, 6343-6346.
21. (b) Enders, D.; Demir, A. S.; Rendenbach, B. E. M. Chem. Ber. 1987, 120, 1731-1735.
22. (c) Martens, J.; Lubben, S. Tetrahedron 1991, 47, 1205-1214.
23. (d) Blarer, S. J.; Seebach, D. Chem. Ber. 1983, 116, 2250-2260.
24. For a seminal reference, see: Stork, G.; Brizzolara, A.; Landesman, H.; Szmuszkovicz, J.; Terrell, R. J. Am. Chem. Soc. 1963, 85, 207-222.
25. For a general discussion of atom economy in organic synthesis, see: (a) Trost, B. M. Science 1991, 254, 1471-1477.
26. (b) Trost, B. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 259-281.
27. (a) Sakthivel, K.; Notz, W.; Bui, T.; Barbas, C. F., III. J. Am. Chem. Soc. 2001, 123, 5260-5267.
28. (b) For a later communication on the same topic, see: List, B.; Pojarliev, P.; Martin, H. Org. Lett. 2001, 3, 2423-2425.
29. Betancort, J. M.; Sakthivel, K.; Thayumanavan, R.; Barbas, C. F., III. Tetrahedron Lett. 2001, 42, 4441-4444.
30. For a recent example of addition of naked aldehydes to electron-deficient olefins in a nonenantioselective manner, see: (a) Hagiwara, H.; Okabe, T.; Hakoda, K.; Hoshi, T.; Ono, H.; Kamat, V. Suzuki, T.; Ando, M. Tetrahedron Lett. 2001, 42, 2705-2707.
31. (b) Hagiwara, H.; Komatsubara, N.; Ono, H.; Okabe, T.; Hoshi, T.; Suzuki, T.; Ando, M.; Kato, M. J. Chem. Soc., Perkin Trans. 1, 2001, 316-322.
32. For previous work from our laboratories in the asymmetric aldol reaction, Mannich reaction, and Robinson annulations through an enamine-type mechanism, see ref 8a and the following, (a) Notz, W.; Sakthivel, K.; Bui, T.; Zhong, G.; Barbas, C. F., III .Tetrahedron Lett. 2001, 42, 199-201.
33. (b) Bui, T.; Barbas, C. F., III. Tetrahedron Lett. 2000, 41, 6951-6954.
34. (c) List, B.; Lerner, R.; Barbas, C. F., III. J. Am. Chem. Soc. 2000, 122, 2395-2396.
35. For a review on stereoselective additions to nitroalkenes, see: Pyne, S. G. In Stereoselective Synthesis, Methods of Organic Chemistry (Houben-Weyl), E21 ed.; Helmchen, G., Hoffmann, R. W., Mulzer, J., Schaumann, E., Eds.: Thieme: Stuttgart New York, 1996; Vol. IV, pp 2161-2176.
36. Diamines were prepared according to the method of Asami. Asami, M. Bull. Chem. Soc. Jpn. 1990, 63, 721-727.
37. In the case of the more reactive substrates such as hexanal, the reaction still proceeded smoothly when the amount of aldehyde was reduced to 5 or 2 equiv or when the catalyst loading was reduced to 10 or 5 mol % to provide the Michael adducts in over 85% yield, though a decrease in dr and ee values associated with longer reaction times was noted.
38. No substantial change of ee and dr in time was observed when employing isovaleraldehyde as donor, but both decreased with longer reaction times when using the smaller homologues such as propionaldehyde.
39. New compounds have been fully characterized spectroscopically, and elemental composition has been established by high-resolution mass speetrometry or combustion analysis.
40. For further details, see the Supporting Information.
41. When (S)-1-(2-pyrrolidinylmethyl)pyrrolidine and 2,4-pentanedione are mixed in equimolar amounts in DMSO, enamine formation is detected through UV spectroscopy. Furthermore, while pyrrolidine itself promotes the Michael reaction, the N-methyl derivative which lacks the secondary amine is ineffective as catalyst. An enamine mechanism is also in accord with our other studies concerning aldol, Mannich, and Michael reactions; see refs 8, 9, and 11.
42. (a) Seebach, D.; Golinski, J. Helv, Chim. Acta 1981, 64, 1413-1423.
43. (b) Blarer, S. J.; Schweizer, W. B.; Seebach, D. Helv: Chim. Acta 1982, 65, 1637-1654.
44. (c) Blarer, S. J.; Seebach, D. Chem. Ber. 1983. 116, 3086-3096.
45. (d) Haner, R.; Laube, T.; Seebach, D. Chimia 1984, 38, 255-257.
46. (e) Seebach, D.; Beck, A. K.; Golinski, J.; Hay, J. N.; Laube, T. Helv. Chim. Acta 1985, 68, 162-172.
47. (f) Seebach, D.; Brook, M. A. Helv. Chim. Acta 1985, 68, 319-324.
48. See refs 5d, 12, 19a, 19b, and 19e. For theoretical studies of the reaction of chiral enamines to electrophilic olefins. see: (a) Sevin, A.; Masure, D.; Giessner-Prettre, C.; Pfau, M. Helv. Chim. Acta 1990, 73, 552-573.
49. (b) Lucero, M. J.; Houk, K. N. J. Am. Chem. Soc. 1997, 119, 826-827 and references therein.
50. Search of the Scifinder database resulted in no hits for the reported γ-formyl nitro compounds.
51. (a) O'Hagan, D. Nat. Prod. Rep. 2000, 17, 435-446.
52. (b) Numata, A.; Ibuka, T. In The Alkaloids; Brossi, A., Ed.: Academic Press: New York, 1987; Vol. 31, Chapter 6.
53. (c) Massiot, Delaude, C. In The Alkaloids; Brossi, A., Ed.: Academic Press: New York, 1986; Vol. 27, Chapter 3.
54. (a) Ling, R.; Ekhato, I. V.; Rubin, J. R.; Wustrow, D. J. Tetrahedron 2001, 57, 6579-6588.
55. (b) Karlsson, S.; Han, F.; Hogberg, H.-E.; Caldirola, P. Tetrahedron: Asymmetry 1999, 10, 2605-2616.
56. (c) Denmark, S. E.; Marcin, L. R. J. Org. Chem. 1995, 60, 3221-3235 and references therein.