Selective access to both diastereoisomers in an enantioselective intramolecular michael reaction by using a single chiral organocatalyst and application in the formal total synthesis of (-)-epibatidine

Chemistry - A European Journal

Volumn 18, Issue 38, 2012, Pages 11913-11918

  Jensen, Kim L ^a   Weise, Christian F ^a   Dickmeiss, Gustav ^a   Morana, Fabio ^a   Davis, Rebecca L ^a   Jørgensen, Karl Anker ^a  

^a AARHUS UNIVERSITY   (Denmark)

Author keywords

asymmetric synthesis; organocatalysis; reaction mechanisms; total synthesis

Indexed keywords

ASYMMETRIC SYNTHESIS; CIS-SELECTIVITY; CYCLOHEXANONES; DFT CALCULATION; DIASTEREOISOMERS; ENANTIOSELECTIVE; EPIBATIDINE; IMINIUM; MECHANISTIC STUDIES; MICHAEL REACTIONS; ORGANOCATALYSIS; ORGANOCATALYSTS; REACTION MECHANISM; TOTAL SYNTHESIS;

ADDITION REACTIONS; DENSITY FUNCTIONAL THEORY; REACTION KINETICS;

ENANTIOSELECTIVITY;

EID: 84866258830     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201202353     Document Type: Article

References (66)

1. Comprehensive Asymmetric Catalysis, Vol.a 1-3 (Eds.:, E.a N. Jacobsen, A. Pfaltz, H. Yamamoto,)., Springer, Berlin, 1999
2. R. Noyori, Asymmetric Catalysis in Organic Synthesis, Wiley, New York, 1994
3. M. J. Gaunt, C. C. C. Johansson, A. McNally, N. T. Vo, Drug Discovery Today 2007, 12, 8
4. C. Grondal, M. Jeanty, D. Enders, Nat. Chem. 2010, 2, 167.
5. M. Raj, G. S. Parashari, V. K. Singh, Adv. Synth. Catal. 2009, 351, 1284
6. J. D. Huber, J. L. Leighton, J. Am. Chem. Soc. 2007, 129, 14552.
7. G. Lu, T. Yoshino, H. Morimoto, S. Matsunaga, M. Shibasaki, Angew. Chem. 2011, 123, 4474
8. Angew. Chem. Int. Ed. 2011, 50, 4382
9. A. Nojiri, N. Kumagai, M. Shibasaki, J. Am. Chem. Soc. 2009, 131, 3779
10. D. A. Evans, D. W. C. MacMillan, D. K. R. Campos, J. Am. Chem. Soc. 1997, 119, 10859; for an example in which the catalyst loading induced a diastereoselectivity switch, see
11. M. Bandini, P. G. Cozzi, A. Umani-Ronchi, Angew. Chem. 2000, 112, 2417
12. Angew. Chem. Int. Ed. 2000, 39, 2327.
13. X.-X. Yan, Q. Peng, Q. Li, K. Zhang, J. Yao, X.-L. Hou, Y.-D. Wu, J. Am. Chem. Soc. 2008, 130, 14362
14. X.-X. Yan, Q. Peng, Y. Zhang, K. Zhang, W. Hong, X.-L. Hou, Y.-D. Wu, Angew. Chem. 2006, 118, 2013
15. Angew. Chem. Int. Ed. 2006, 45, 1979.
16. For general reviews on organocatalysis, see
17. D. W. C. MacMillan, Nature 2008, 455, 304
18. J. L. Vicario, D. Badía, L. Carrillo, Synthesis 2007, 2065
19. Enantioselective Organocatalysis, (Ed.:, P.a I. Dalko,), Wiley-VCH, Weinheim, Germany, 2007; see special issue 12 on organocatalysis (Ed. B. List)
20. Chem. Rev. 2007, 107, 5413
21. Asymmetric Organocatalysis (Eds.:, A. Berkessel, H. Gröger,), Wiley-VCH, Weinheim, Germany 2004; for reviews on aminocatalysis, see
22. K. L. Jensen, G. Dickmeiss, H. Jiang, Å. Albrecht, K. A. Jørgensen, Acc. Chem. Res. 2012, 45, 248
23. P. Melchiorre, M. Marigo, A. Carlone, G. Bartoli, Angew. Chem. 2008, 120, 6232
24. Angew. Chem. Int. Ed. 2008, 47, 6138
25. A. Dondoni, A. Massi, Angew. Chem. 2008, 120, 4716
26. Angew. Chem. Int. Ed. 2008, 47, 4638
27. G. Lelais, D. W. C. MacMillan, Aldrichimica Acta 2006, 39, 79.
28. For an example in which two aminocatalysts are used in a tandem fashion to control the diastereoselectivity, see
29. B. Simmons, A. M. Walji, D. W. C. MacMillan, Angew. Chem. 2009, 121, 4413
30. Angew. Chem. Int. Ed. 2009, 48, 4349; for an example in which proline and 3-pyrrolidinecarboxylic acid afford opposite diastereoselectivity, see
31. H. Zhang, F. Mifsud, F. Tanaka, C. F. Barbas III, J. Am. Chem. Soc. 2006, 128, 9630; for an example in which proline and an axially chiral diamine afford opposite diastereoselectivity, see
32. T. Kano, R. Sakamoto, M. Akakura, K. Maruoka, J. Am. Chem. Soc. 2012, 134, 7516; for syn-selective Mannich reaction with aldehydes, see
33. A. Cõrdova, S. Watanabe, F. Tanaka, W. Notz, C. F. Barbas III, J. Am. Chem. Soc. 2002, 124, 1866; for anti-selective examples, see
34. S. Mitsumori, H. Zhang, P. H.-Y. Cheong, K. N. Houk, F. Tanaka, C. F. Barbas III, J. Am. Chem. Soc. 2006, 128, 1040
35. T. Kano, Y. Yamaguchi, O. Tokuda, K. Maruoka, J. Am. Chem. Soc. 2005, 127, 16408; for examples in which two different hydrogen-bonding catalysts induce opposite diastereoselectivity, see
36. B. Wang, F. Wu, Y. Wang, X. Liu, L. Deng, J. Am. Chem. Soc. 2007, 129, 768
37. Y. Wang, H. Li, Y.-Q. Wang, Y. Liu, B. M. Foxman, L. Deng, J. Am. Chem. Soc. 2007, 129, 6364.
38. X. Tian, C. Cassani, Y. Liu, A. Moran, A. Urakawa, P. Galzerano, E. Arceo, P. Melchiorre, J. Am. Chem. Soc. 2011, 133, 17934.
39. For an example on a diastereoselectivity switch based on an acidic additive in an aldol reaction, see:, J. Gao, S. Bai, Q. Gao, Y. Liu, Q. Yang, Chem. Commun. 2011, 47, 6716.
40. For examples of epimerization of nitro stereocenters after subsequent base addition, see
41. H. Uehara, R. Imashiro, G. Hernández-Torres, C. F. Barbas III, Proc. Natl. Acad. Sci. USA 2010, 107, 20672
42. T. Hayashi, T. Senda, M. Ogasawara, J. Am. Chem. Soc. 2000, 122, 10716
43. L. Guo, Y. Chi, A. M. Almeida, I. A. Guzei, B. K. Parker, S. H. Gellman, J. Am. Chem. Soc. 2009, 131, 16018.
44. P. Perlmutter, Conjugate Addition Reactions in Organic Synthesis, Pergamon Press, Oxford, 1992
45. R. Ballini, G. Bosica, D. Fiorini, A. Palmieri, M. Petrini, Chem. Rev. 2005, 105, 933.
46. For reviews on the applications of cinchona-based primary amines, see
47. L. Jiang, Y.-C. Chen, Catal. Sci. Technol. 2011, 1, 354
48. G. Bartoli, P. Melchiorre, Synlett 2008, 1759.
49. For representative reviews on asymmetric organocatalytic Michael reactions, see
50. D. Almasi, D. A. Alonso, C. Nájera, Tetrahedron: Asymmetry 2007, 18, 299
51. S. B. Tsogoeva, Eur. J. Org. Chem. 2007, 1701.
52. For an intramolecular Michael addition to conjugated esters, see
53. W. J. Nodes, D. R. Nutt, A. M. Chippindale, A. J. A. Cobb, J. Am. Chem. Soc. 2009, 131, 16016; for an example based on a cascade reaction resulting in similar products, see
54. L.-Y. Wu, G. Bencivenni, M. Mancinelli, A. Mazzanti, G. Bartoli, P. Melchiorre, Angew. Chem. 2009, 121, 7332
55. Angew. Chem. Int. Ed. 2009, 48, 7196.
56. 3 was necessary for some substrates.
57. 1Ha NMR spectrum at that time.
58. Retro-Michael/Michael seems unlikely, because treatment of the product 4 a with pseudo-enantiomeric catalyst 2 b did not deteriorate the enantiopurity of the product. Other bases led to decomposition of the cis-product.
59. Calculations were performed with Gaussiana 09 (Gaussiana 09, Revisiona A.02, M.a J. Frisch, G.a W. Trucks, H.a B. Schlegel, G.a E. Scuseria, M.a A. Robb, J.a R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.a A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H.a P. Hratchian, A.a F. Izmaylov, J. Bloino, G. Zheng, J.a L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J.a A. Montgomery, Jr., J.a E. Peralta, F. Ogliaro, M. Bearpark, J.a J. Heyd, E. Brothers, K.a N. Kudin, V.a N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.a C. Burant, S.a S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.a M. Millam, M. Klene, J.a E. Knox, J.a B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.a E. Stratmann, O. Yazyev, A.a J. Austin, R. Cammi, C. Pomelli, J.a W. Ochterski, R.a L. Martin, K. Morokuma, V.a G. Zakrzewski, G.a A. Voth, P. Salvador, J.a J. Dannenberg, S. Dapprich, A.a D. Daniels, Ö. Farkas, J.a B. Foresman, J.a V. Ortiz, J. Cioslowski, D.a J. Fox, Gaussian, Inc., Wallingford CT, 2009). Geometries were optimized with the M06-2x/6-31+G(d,p) level of theory and basis set
60. 3OH (ε=32.613). See the Supporting Information for full details and complete references on theoretical methods.
61. For coordinates and energies of all intermediates and transition state structures, see the Supporting Information.
62. -1 higher in energy than I. Cyclization of II to III was also found to be energetically unfavorable. Thus, it seems unlikely that the reaction proceeds through this cyclization pathway.
63. CCDCa 878386 (3 b) and 878387 (ent- 4 b) contain 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.
64. For a comprehensive review, see:, H. F. Olivo, M. S. Hemenway, Org. Prep. Proced. Int. 2002, 34, 1.
65. C. Szántay, Z. Kardos-Balogh, I. Moldvai, C. Szántay Jr., E. Temesvári-Major, G. Blaskõ, Tetrahedron 1996, 52, 11053.
66. For another epibatidine synthesis (10 steps) by using hydrogen-bonding catalysis (75 %a ee), see:, Y. Hoashi, T. Yabuta, Y. Takemoto, Tetrahedron Lett. 2004, 45, 9185.