A highly enantioselective intramolecular Michael reaction catalyzed by N-heterocyclic carbenes

Angewandte Chemie - International Edition

Volumn 46, Issue 17, 2007, Pages 3107-3110

  Phillips, Eric M ^a   Wadamoto, Manabu ^a   Chan, Audrey ^a   Scheidt, Karl A ^a  

^a NORTHWESTERN UNIVERSITY   (United States)

Author keywords

Acylation; Asymmetric catalysis; Michael addition; N heterocyclic carbenes; Synthetic methods

Indexed keywords

ADDITION REACTIONS; CATALYST ACTIVITY; ENANTIOSELECTIVITY; MOLECULAR INTERACTIONS; REACTION KINETICS; SUBSTITUTION REACTIONS;

ASYMMETRIC CATALYSIS; MICHAEL ADDITION; N-HETEROCYCLIC CARBENES; SYNTHETIC METHODS;

ORGANIC CARBON;

AMIDE; CARBENE; DRUG DERIVATIVE; HETEROCYCLIC COMPOUND; HYDROCARBON; METHANE;

ACETYLATION; ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; STEREOISOMERISM;

ACETYLATION; AMIDES; CATALYSIS; HETEROCYCLIC COMPOUNDS; HYDROCARBONS; METHANE; MOLECULAR STRUCTURE; STEREOISOMERISM;

EID: 34250822311     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200605235     Document Type: Article

References (55)

1. a) A. Michael, J. Prakt. Chem. 1887, 36, 349-356;
2. b) E. D. Bergmann, D. Ginsburg, R. Pappo, Org. React. 1959, 10, 179-555;
3. c) D. A. Oare, C. A. Heathcock, In Topics in Stereochemistry, Vol. 20 (Eds.: E. L. Eliel, S. H. Wilen), Wiley, New York, 1991, pp. 124-170;
4. d) R. D. Little, M. R. Masjedizadeh, Org. React. 1995, 47, 315-552;
5. e) N. Krause, A. Hoffmann-Röder, Synthesis 2001, 171 -196.
6. a) K. Narasaka, K, Soai, T. Mukaiyama, Chem. Lett. 1974, 1223-1224;
7. b) T. Mukaiyama, S. Kobayashi, Org. React. 1994, 46, 1-103;
8. c) D. A. Evans, K. A. Scheidt, J. N. Johnston, M. C. Willis, J. Am. Chem. Soc. 2001, 123, 4480-4491, and references therein;
9. d) Comprehensive Asymmetric Catalysis (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, New York, 1999, chap. 31.
10. a) M. Yamaguchi, T. Shiraishi, M. Hirama, Angew. Chem. 1993, 105, 1243-1245;
11. Angew. Chem. Int. Ed. Engl. 1993, 32, 1176-1178;
12. b) M. Yamaguchi, T. Shiraishi, M. Hirama, J. Org. Chem. 1996, 61, 3520-3530.
13. S. P. Brown, N. C. Goodwin, D. W. C. MacMillan, J. Am. Chem. Soc. 2003, 125, 1192-1194.
14. a) P. Melchiorre, K. A. Jørgensen, J. Org. Chem. 2003, 68, 4151-4157;
15. b) N. Halland, P. S. Aburel, K. A. Jørgensen, Angew. Chem. 2003, 115, 685-689;
16. Angew. Chem. Int. Ed. 2003, 42, 661-665;
17. c) N. Halland, P. S. Aburel, K. A. Jørgensen, Angew. Chem. 2004, 116, 1292-1297;
18. Angew. Chem. Int. Ed. 2004, 43, 1272-1277.
19. a) B. List, Tetrahedron 2002, 58, 5573-5590;
20. b) M. T. Hechavarria Fonseca, B. List, Angew. Chem. 2004, 116, 4048-4050;
21. Angew. Chem. Int. Ed. 2004, 43, 3958-3960;
22. c) For an excellent review of enamine catalysis, see: B. List, Acc. Chem. Res. 2004, 37, 548-557.
23. For examples of metal-catalyzed enolate generation, see: a) N. Yoshikawa, Y. M. A. Yamada, J. Das, H. Sasai, M. Shibasaki, J. Am. Chem. Soc. 1999, 121, 4168-4178;
24. b) B. M. Trost, H. Ito, J. Am. Chem. Soc. 2000, 122, 12003-12004;
25. c) D. A. Evans, J. S. Tedrow, J. T. Shaw, C. W. Downey, J. Am. Chem. Soc. 2002, 124, 392-393;
26. d) D. A. Evans, R. J. Thomson, J. Am. Chem. Soc. 2005, 127, 10506-10507.
27. For examples of amine-catalyzed enamine generation, see: a) B. List, R. A. Lerner, C. F. Barbas III, J. Am. Chem. Soc. 2000,122, 2395-2396;
28. b) J. M. Betancort, K. Sakthivel, R. Thayumanavan, C. F. Barbas III, Tetrahedron Lett. 2001, 42, 4441-4444;
29. c) B. List, Synlett 2001, 1675 -1686;
30. d) P. I. Dalko, L. Moisan, Angew. Chem. 2001, 113, 3840-3864;
31. Angew. Chem. Int. Ed. 2001, 40, 3726-3748;
32. e) B. List, Tetrahedron 2002, 58, 5573-5590;
33. f) Y. Hayashi, H. Gotoh, T. Tamura, H. Yamaguchi, R. Masui, M. Shoji, J. Am. Chem. Soc. 2005,127, 16028-16029.
34. a) A. E. Mattson, A. R. Bharadwaj, K. A. Scheidt, J. Am. Chem. Soc. 2004, 126, 2314;
35. b) A. R. Bharadwaj, K. A. Scheidt, Org. Lett. 2004, 6, 2465;
36. c) A. E. Mattson, K. A. Scheidt, Org. Lett. 2004, 6, 4363;
37. d) M. C. Myers, A. R. Bharadwaj, B. C. Milgram, K. A. Scheidt, J. Am. Chem. Soc. 2005, 127, 14675;
38. e) A. Chan, K. A. Scheidt, Org. Lett. 2005, 7, 905;
39. f) A. Chan, K. A. Scheidt, J. Am. Chem. Soc. 2006, 128, 4558.
40. Enols have also been implemented as intermediates in reactions that combine NHCs and aldehydes; see: a) N. T. Reynolds, T. Rovis, J. Am. Chem. Soc. 2005, 127, 16406-16407;
41. b) M. He, J. R. Struble, J. W. Bode, J. Am. Chem. Soc. 2006, 128, 8418-8420.
42. The potential hetero-Diels-Alder pathway is unlikely given the constrained nature of the intramolecular substrates and the high levels of cis diastereoselectivity. For a related intermolecular process using triazolium salt D as the precatalyst which invokes a hetero-Diels-Alder pathway, see: M. He, G. J. Uc, J. W. Bode, J. Am. Chem. Soc. 2006, 128, 15088-15089.
43. The high diastereoselectivity in this reaction may arise because of a reversible Michael reaction followed by an irreversible lactonization occurring through the cis isomer. Investigations of these mechanistic pathways are ongoing.
44. For an approach to the trans diastereomers of compounds such as 4 using the Hantzsch ester and a chiral secondary amine, see J. W. Yang, M. T. H. Fonseca, B. List, J. Am. Chem. Soc. 2005, 127, 15036-15037.
45. See Ref [10b]. For relevant examples of chiral triazolium salts used in asymmetric catalysis, see: a) D. Enders, K. Breuer, J. Runsink, J. H. Teles, Helv. Chim. Acta 1996, 79, 1899-1902;
46. b) M. S. Kerr, J. R. de Alaniz, T. Rovis, J. Am. Chem. Soc. 2002, 124, 10298-10299;
47. c) D. Enders, U. Kallfass, Angew. Chem. 2002, 114, 1822-1824;
48. Angew. Chem. Int. Ed. 2002, 41, 1743;
49. d) N. T. Reynolds, J. R. de Alaniz, T. Rovis, J. Am. Chem. Soc. 2004, 126, 9518;
50. e) D. Enders, T. Balensiefer, Acc. Chem. Res. 2004, 37, 534;
51. f) J. R. de Alaniz, T. Rovis, J. Am. Chem. Soc. 2005, 127, 6284;
52. g) D. Enders, O. Niemeier, T. Balensiefer, Angew. Chem. 2006, 118, 1491;
53. Angew. Chem. Int. Ed. 2006, 45, 1463.
54. The remaining mass balance is primarily the five-membered ring which resulted from the conjugate addition of the homoenolate formed in situ.
55. CCDC-631931 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam. ac.uk/data_request/cif.