Solvent-dependent enantiodivergent mannich-type reaction: Utilizing a conformationally flexible guanidine/bisthiourea organocatalyst

Angewandte Chemie - International Edition

Volumn 49, Issue 48, 2010, Pages 9254-9257

  Sohtome, Yoshihiro ^a   Tanaka, Shinji ^a   Takada, Keisuke ^a   Yamaguchi, Takahisa ^a   Nagasawa, Kazuo ^a  

^a TOKYO UNIVERSITY OF AGRICULTURE AND TECHNOLOGY   (Japan)

Author keywords

asymmetric synthesis; enantiodivergent catalysis; enthalpy; entropy; organocatalysis

Indexed keywords

ASYMMETRIC SYNTHESIS; ENANTIODIVERGENT CATALYSIS; ENTHALPY-ENTROPY COMPENSATION; KINETIC ANALYSIS; MALONATES; MANNICH-TYPE REACTIONS; ORGANOCATALYSIS; ORGANOCATALYSTS;

ENANTIOMERS; ENTHALPY; ENTROPY; RATE CONSTANTS; REACTION KINETICS; SYNTHESIS (CHEMICAL);

CATALYSIS;

GUANIDINE; IMINE; SOLVENT; THIOUREA;

ARTICLE; CATALYSIS; CHEMISTRY; CONFORMATION; STEREOISOMERISM;

CATALYSIS; GUANIDINE; IMINES; MOLECULAR CONFORMATION; SOLVENTS; STEREOISOMERISM; THIOUREA;

EID: 78649588441     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201005109     Document Type: Article

References (92)

1. For selected recent reviews on asymmetric hydrogen-bond donor catalysis, see
2. P. M. Pihko, Hydrogen Bonding in Organic Synthesis, Wiley-VCH, Weinheim, 2009
3. Z. Zhang, P. R. Schreiner, Chem. Soc. Rev. 2009, 38, 1187
4. A. G. Doyle, E. N. Jacobsen, Chem. Rev. 2007, 107, 5713
5. S. J. Connon, Chem. Eur. J. 2006, 12, 5418
6. M. S. Taylor, E. N. Jacobsen, Angew. Chem. 2006, 118, 1550
7. Angew. Chem. Int. Ed. 2006, 45, 1520.
8. For selected reviews on asymmetric organocatalysis, see
9. A. Berkessel, H. Gröger, Asymmetric Organocatalysis, Wiley-VCH, Weinheim, 2005
10. Enantioselective Organocatalysis: Reaction and Experimental Procedures (Ed.:, P. I. Dalko,), Wiley, New York, 2007
11. D. W. C. MacMillan, Nature 2008, 455, 304.
12. For selected recent reviews on guanidine and guanidinium organocatalysts, see
13. T. Ishikawa, Superbases for Organic Syntheis, Wiley, New York, 2009
14. D. Leow, C.-H. Tan, Chem. Asian J. 2009, 4, 488
15. T. Ishikawa, T. Kumamoto, Synthesis 2006, 737.
16. For pioneering work utilizing chiral urea/thiourea catalysts, see:, M. S. Sigman, E. N. Jacobsen, J. Am. Chem. Soc. 1998, 120, 4901; for other works by Jacobsen and his co-workers, see references [1] and [2].
17. For original work, see
18. T. Okino, Y. Hoashi, Y. Takemoto, J. Am. Chem. Soc. 2003, 125, 12672; for other work by Takemoto and co-workers, see references [4] and [5] as well as their review
19. M. Miyabe, Y. Takemoto, Bull. Chem. Soc. Jpn. 2008, 81, 785.
20. For pioneering work utilizing chiral peptide catalysts, see
21. S. J. Miller, G. T. Copeland, N. Papaioannou, T. E. Horstmann, E. M. Ruel, J. Am. Chem. Soc. 1998, 120, 1629; for a recent review on peptide catalysts, see
22. E. A. C. Davie, S. M. Mennen, Y. Xu, S. J. Miller, Chem. Rev. 2007, 107, 5759.
23. For a report on guanidinium/bisthiourea organocatalysis, see
24. Y. Sohtome, Y. Hashimoto, K, Nagasawa, Adv. Synth. Catal. 2005, 347, 1643; for a recent review, see
25. Y. Sohtome, K. Nagasawa, Synlett 2010, 1.
26. Y. Sohtome, B. Shin, N. Horitsugi, R. Takagi, K. Noguchi, K. Nagasawa, Angew. Chem. 2010, 122, 7457
27. Angew. Chem. Int. Ed. 2010, 49, 7299.
28. For a review, see
29. Y. Inoue, N. Sugahara, T. Wada, Pure Appl. Chem. 2001, 73, 475; for work concerning on entropy-associated photochemical reactions
30. Y. Inoue, T. Yokoyama, N. Yamasaki, A. Tai, Nature 1989, 341, 225.
31. For reviews, see
32. Y. H. Kim, Acc. Chem. Res. 2001, 34, 955
33. M. P. Sibi, M. Liu, Curr. Org. Chem. 2001, 5, 719
34. G. Zanoni, F. Castronovo, M. Franzini, G. Vidari, E. Giannini, Chem. Soc. Rev. 2003, 32, 115
35. M. Hayashi, T. Tanaka, Synthesis 2008, 3361
36. M. Batók, Chem. Rev. 2010, 110, 1663.
37. S. Yamaguchi, S. H. Mosher, J. Am. Chem. Soc. 1972, 94, 9254
38. S. Yamaguchi, S. H. Mosher, J. Org. Chem. 1973, 38, 1870.
39. For a recent example, see:, A. Nojiri, N. Kumagai, M. Shibasaki, J. Am. Chem. Soc. 2009, 131, 3779 and references are cited therein.
40. P. Manzón, R. Chinchilla, C. Nájera, G. Guillena, R. Kreiter, R. J. M. K. Gebbink, G. van Koten, Tetrahedron: Asymmetry 2002, 13, 2181
41. J. E. Imbriglio, M. M. Vasbinder, S. J. Miller, Org. Lett. 2003, 5, 3741
42. S.-H. Chen, B.-C. Hong, C.-F. Su, S. Sarshar, Tetrahedron Lett. 2005, 46, 8899
43. N. Abermi, G. Masson, J. Zhu, Org. Lett. 2009, 11, 4648
44. N. Abermi, G. Masson, J. Zhu, Adv. Synth. Catal. 2010, 352, 656.
45. For enantiodivergent reactions using stoichiometric amounts of a chiral organic compound, see
46. S. Arseniyadis, A. Valleix, A. Wagner, C. Mioskowski, Angew. Chem. 2004, 116, 3376
47. Angew. Chem. Int. Ed. 2004, 43, 3314
48. S. Arseniyadies, P. V. Subhash, A. Valleix, S. P. Mathew, D. G. Blackmond, A. Wagner, C. Mioskowski, J. Am. Chem. Soc. 2005, 127, 6138.
49. For general reviews on catalytic asymmetric Mannich-type reaction, see
50. A. Ting, S. E. Schaus, Eur. J. Org. Chem. 2007, 5797
51. J. M. Verkade, J. C. van Hemert, P. L. M. Quaedflieg, F. J. T. Rutjes, Chem. Soc. Rev. 2008, 37, 29.
52. For selected examples of organocatalytic asymmetric Mannich-type reactions using 1,3-dicarbonyl compounds with thiourea/tert-amine catalyst, see
53. Y. Yamaoka, H. Miyabe, Y. Yasui, Y. Takemoto, Synthesis 2007, 2571; with phosphoric acid
54. D, Uraguchi, M, Terada, J. Am. Chem. Soc. 2004, 126, 5356; with cinchona alkaloids
55. S. Lou, B. M. Taoka, A. Ting, S. E. Schaus, J. Am. Chem. Soc. 2005, 127, 11256
56. A. Ting, S. Lou, S. E. Schaus, Org. Lett. 2006, 8, 2003
57. S. Lou, P. Dai, S. E. Schaus, J. Org. Chem. 2007, 72, 9998
58. F. Fini, L. Bernardi, R. P. Herrera, D. Pettersen, A. Ricci, V. Sgarzani, Adv. Synth. Catal. 2006, 348, 2043
59. O. Marianacci, G. Micheletti, L. Bernardi, F. Fini, M. Fochi, D. Pettersen, V. Sgarzani, A. Ricci, Chem. Eur. J. 2007, 13, 8388; with chincona-based thiourea
60. J. Song, Y. Wang, L. Deng, J. Am. Chem. Soc. 2006, 128, 6048
61. J. Song, H.-W. Shih, L. Deng, Org. Lett. 2007, 9, 603
62. A. L. Tillman, J. Ye, D. J. Dixon, Chem. Commun. 2006, 1191
63. C. M. Bode, A. Ting, S. E. Schaus, Tetrahedron 2006, 62, 11499.
64. K. Takada, S. Tanaka, K. Nagasawa, Synlett 2009, 1643.
65. See the Supporting Information for details.
66. In this report, we defined the ee value of (S)- 4 as plus and that of (R)- 4 as minus.
67. For selected examples of solvent-dependent enantiodivergent catalysis, see
68. M. Kanai, K. Koga, K. Tomioka, J. Chem. Soc. Chem. Commun. 1993, 1248
69. K. Tani, J. Onouchi, T. Yamagata, Y. Kataoka, Chem. Lett. 1995, 955
70. B. M. Trost, F. D. Toste, J. Am. Chem. Soc. 1999, 121, 4545
71. Y. Inoue, H. Ikeda, M. Kaneda, T. Sumimura, S. R. L. Everitt, T. Wada, J. Am. Chem. Soc. 2000, 122, 406
72. J. Zhou, M.-C. Ye, Z.-Z. Huang, Y. Tang, J. Org. Chem. 2004, 69, 1309.
73. ≠) in supramolecular complexation:, M. Rekharsky, Y. Inoue, J. Am. Chem. Soc. 2000, 122, 4418.
74. H. Eyring, J. Chem. Phys. 1935, 3, 107.
75. For selected reviews concerning the temperature dependence of asymmetric transformations, see reference [8a] as well as
76. G. A. Hembury, V. V. Borovkov, Y. Inoue, Chem. Rev. 2008, 108, 1
77. D. Heller, H. Buschmann, Top. Catal. 1998, 5, 159
78. Y. Inoue, Chem. Rev. 1992, 92, 741
79. H. Buschmann, H.-D. Scharf, N. Hoffmann, P. Esser, Angew. Chem. 1991, 103, 480
80. Angew. Chem. Int. Ed. Engl. 1991, 30, 477.
81. ≠) in enantioselective catalysis, see
82. I. Tóth, I. Guo, B. E. Hanson, Organometallics 1993, 12, 848
83. J. Otera, K. Sakamoto, T. Tsukamoto, A. Orita, Tetrahedron Lett. 1998, 39, 3201
84. T. Nishida, A. Miyafuji, N. Y. Ito, T. Katsuki, Tetrahedron Lett. 2000, 41, 7053
85. D. Enders, E. C. Ullrich, Tetrahedron: Asymmetry 2000, 11, 3861
86. R. R. Knowles, S. Lin, E. N. Jacobsen, J. Am. Chem. Soc. 2010, 132, 5030.
87. ≠ gave rise to a reasonably straight line. In several reports, linear relationships in the enthalpy-entropy compensation plots have been used to indicate that a single electrostatic interaction mode is operative in the complexation processes. See the Supporting Information for details as well as
88. J. E. Leffler, E. Grunwald, Rates and Equilibria of Organic Reactions, Wiley, New York, 1963; for a recent example of a photochemical reaction, see
89. G. Fukahara, T. Mori, Y. Inoue, J. Org. Chem. 2009, 74, 6714; and references cited therein; for an example of asymmetric reduction of α-ketoesters with chiral NADH model, see
90. R. Saito, S. Naruse, K. Takano, K. Fukuda, A. Katoh, Y. Inoue, Org. Lett. 2006, 8, 2067; for a selected example of chromatography, see
91. J. Li, P. W. Carr, J. Chromatogr. A 1994, 670, 105.
92. See the Supporting Information for preliminary mechanistic studies.