A chiral primary amine thiourea catalyst for the highly enantioselective direct conjugate addition of α,α-disubstituted aldehydes to nitroalkenes

Angewandte Chemie - International Edition

Volumn 45, Issue 38, 2006, Pages 6366-6370

  Lalonde, Mathieu P ^a   Chen, Yonggang ^a   Jacobsen, Eric N ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

Amines; Asymmetric catalysis; Conjugate addition; Organocatalysis

Indexed keywords

ASYMMETRIC CATALYSIS; CONJUGATE ADDITION; NUCLEOPHILES; ORGANOCATALYSIS;

ACTIVATION ANALYSIS; ADDITION REACTIONS; CATALYSTS; CHEMICAL ACTIVATION; SUBSTITUTION REACTIONS;

ALDEHYDES;

ALDEHYDE; ALKENE; AMINE; NITRO DERIVATIVE; THIOUREA;

ARTICLE; CATALYSIS; CHEMICAL MODEL; CHEMICAL STRUCTURE; CHEMISTRY; METABOLISM; STEREOISOMERISM; SYNTHESIS;

ALDEHYDES; ALKENES; AMINES; CATALYSIS; MODELS, CHEMICAL; MOLECULAR STRUCTURE; NITRO COMPOUNDS; STEREOISOMERISM; THIOUREA;

EID: 33749340635     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200602221     Document Type: Article

References (100)

1. For a timely review, see: B. List, Chem. Commun. 2006, 819-824.
2. a) S. Pizzarello, A. L. Weber, Science 2004, 303, 1151;
3. b) F. Tanaka, R. Thayumanavan, N. Mase, C. F. Barbas III, Tetrahedron Lett. 2004, 45, 325-328;
4. c) A. Córdova, I. Ibrahem, J. Casas, H. Sundén, M. Engqvist, E. Reyes, Chem. Eur. J. 2005, 11, 4772-4784;
5. d) M. Amedjkouh, Tetrahedron: Asymmetry 2005, 16, 1411-1414;
6. e) A. Córdova, W. Zou, I. Ibrahem, E. Reyes, M. Engqvist, W.-W. Liao, Chem. Commun. 2005, 3586-3588;
7. f) W. Zou, I. Ibrahem, P. Dziedzic, H. Sundén, A. Córdova, Chem. Commun. 2005, 4946-4948;
8. g) I. Ibrahem, W. Zou, M. Engqvist, Y. Xu, A. Córdova, Chem. Eur. J. 2005, 11, 7024-7029;
9. h) A. Bassan, W. Zou, E. Reyes, F. Himo, A. Córdova, Angew. Chem. 2005, 117, 7190-7194;
10. Angew. Chem. Int. Ed. 2005, 44, 7028-7032;
11. i) Y. Xu, A. Córdova, Chem. Commun. 2006, 460-462;
12. j) Y. Xu, W. Zou, H. Sundén, I. Ibrahem, A. Córdova, Adv. Synth. Catal. 2006, 348, 418-424.
13. a) E. D. Bergmann, E. Zimkin, S. Pinchas, Rec. Trav. Chim. 1952, 71, 168-191;
14. b) E. D. Bergmann, Y. Hirshberg, E. Zimkin, S. Pinchas, Rec. Trav. Chim. 1952, 71, 192-199;
15. c) E. D. Bergmann, E. Meeron, Y. Hirshberg, S. Pinchas, Rec. Trav. Chim. 1952, 71, 200-212;
16. d) B. Witkop, J. Am. Chem. Soc. 1956, 78, 2873-2882;
17. e) M. Pfau, C. Ribière, J. Chem. Soc. D 1970, 66-67;
18. f) R. A. Clark, D. C. Parker, J. Am. Chem. Soc. 1971, 93, 7257-7261;
19. g) B. De Jeso, J.-C. Pommier, J. Chem. Soc. Chem. Commun. 1977, 565-566;
20. h) B. De Jeso, J.-C. Pommier, J. Organomet. Chem. 1977, 137, 23-29;
21. i) R. Knorr, A. Weiss, P. Löw, E. Räpple, Chem. Ber. 1980, 113, 2462-2489;
22. j) D. R. Boyd, W. B. Jennings, L. C. Waring, J. Org. Chem. 1986, 51, 992-995;
23. k) B. Capon, Z.-P. Wu, J. Org. Chem. 1990, 55, 2317-2324.
24. D. J. Hupe in New Comprehensive Biochemistry, Vol. 6 (Ed.: M. I. Page), Elsevier, Amsterdam, 1984, pp. 271-301.
25. a) T. Okino, Y. Hoashi, Y. Takemoto, J. Am. Chem. Soc. 2003, 125, 12 672-12 673;
26. b) T. Okino, S. Nakamura, T. Furukawa, Y. Takemoto, Org. Lett. 2004, 6, 625-627;
27. c) Y. Hoashi, T. Yabuta, Y. Takemoto, Tetrahedron Lett. 2004, 45, 9185-9188;
28. d) T. Okino, Y. Hoashi, T. Furukawa, X. Xu, Y. Takemoto, J. Am. Chem. Soc. 2005, 127, 119-125;
29. e) A. Berkessel, F. Cleemann, S. Mukherjee, T. N. Müller, J. Lex, Angew. Chem. 2005, 117, 817-821;
30. Angew. Chem. Int. Ed. 2005, 44, 807-811;
31. f) Y. Hoashi, T. Okino, Y. Takemoto, Angew. Chem. 2005, 117, 4100-4103;
32. Angew. Chem. Int. Ed. 2005, 44, 4032-4035;
33. g) A. Berkessel, F. Cleemann, S. Mukherjee, Angew. Chem. 2005, 117, 7632-7635;
34. Angew. Chem. Int. Ed. 2005, 44, 7466-7469;
35. h) A. Berkessel, S. Mukherjee, F. Cleemann, T. N. Müller, J. Lex, Chem. Commun. 2005, 1898-1900;
36. i) A. P. Dove, R. C. Pratt, B. G. G. Lohmeijer, R. M. Waymouth, J. L. Hedrick, J. Am. Chem. Soc. 2005, 127, 13 798-13 799;
37. j) B. Vakulya, S. Varga, A. Csámpal, T. Soós, Org. Lett. 2005, 7, 1967-1969;
38. k) B.-J. Li, L. Jiang, M. Liu, Y.-C. Chen, L.-S. Ding, Y. Wu, Synlett 2005, 603-606;
39. l) S. H. McCooey, S. J. Connon, Angew. Chem. 2005, 117, 6525-6528;
40. Angew. Chem. Int. Ed. 2005, 44, 6367-6370;
41. m) J. Ye, D. J. Dixon, P. S. Hynes, Chem. Commun. 2005, 4481-4483;
42. n) D. E. Fuerst, E. N. Jacobsen, J. Am. Chem. Soc. 2005, 127, 8964-8965;
43. o) J. Wang, H. Li, X. Yu, L. Zu, W. Wang, Org. Lett. 2005, 7, 4293-4296;
44. p) J. Wang, H. Li, W. Duan, L. Zu, W. Wang, Org. Lett. 2005, 7, 4713-4716;
45. q) X. Xu, T. Furukawa, T. Okino, H. Miyabe, Y. Takemoto, Chem. Eur. J. 2006, 12, 466-476.
46. For reviews concerning asymmetric catalysis by chiral thioureas (including tertiary amine thiourea derivatives), see: a) S. J. Connon, Chem. Eur. J. 2006, 12, 5418-5427;
47. b) M. S. Taylor, E. N. Jacobsen, Angew. Chem. 2006, 118, 1550-1573;
48. Angew. Chem. Int. Ed. 2006, 45, 1520-1543;
49. c) P. R. Schreiner, Chem. Soc. Rev. 2003, 32, 289-296;
50. d) Y. Takemoto, Org. Biomol. Chem. 2005, 3, 4299-4306.
51. Although thorough mechanistic investigations have as yet not been reported, tertiary amine thiourea catalysts are generally proposed to function by cooperative general acid/general base mechanisms reminiscent of more complex enzymatic systems, wherein reactivity and selectivity are imparted through binding, activation, and proper positioning of distinct substrates. For a discussion of the aforementioned concepts in enzyme catalysis, see: a) T. C. Bruice in Enzymes, Vol. 2, 3rd ed. (Ed.: P. D. Boyer), Academic Press, New York, 1970, pp. 217-279; b) R. A. Copeland, Enzymes: A Practical Introduction to Structure, Mechanism, and Data Analysis, 2nd ed., Wiley, New York, 2000, pp. 146-187.
52. a) S. B. Tsogoeva, S. Wei, Chem. Commun. 2006, 1451-1453;
53. b) H. Huang, E. N. Jacobsen, J. Am. Chem. Soc. 2006, 128, 7170-7171.
54. J. d'Angelo, D. Desmaële, F. Dumas, A. Guingant, Tetrahedron: Asymmetry 1992, 3, 459-505, and references therein.
55. For alternative asymmetric catalytic approaches to the preparation of compounds with contiguous quaternary and tertiary stereogenic centers, see: a) Y. Hamashima, D. Hota, M. Sodeoka, J. Am. Chem. Soc. 2002, 124, 11 240-11 241;
56. b) M. S. Taylor, E. N. Jacobsen, J. Am. Chem. Soc. 2003, 125, 11 204-11 205;
57. c) M. S. Taylor, D. N. Zalatan, A. M. Lerchner, E. N. Jacobsen, J. Am. Chem. Soc. 2005, 127, 1313-1317;
58. d) H. Li, Y. Wang, L. Tang, F. Wu, X. Liu, C. Guo, B. M. Foxman, L. Deng, Angew. Chem. 2005, 117, 107-110;
59. Angew. Chem. Int. Ed. 2005, 44, 105-108;
60. e) F. Wu, H. Li, L. Deng, Angew. Chem. 2006, 118, 961-964;
61. Angew. Chem. Int. Ed. 2006, 45, 947-950.
62. For secondary amine catalyzed additions of unbranched aldehydes to nitroalkenes, see: a) J. M. Betancort, C. F. Barbas III, Org. Lett. 2001, 3, 3737-3740;
63. b) A. Alexakis, O. Andrey, Org. Lett. 2002, 4, 3611-3614;
64. c) O. Andrey, A. Alexakis, A. Tomassini, G. Bernardinelli, Adv. Synth. Catal. 2004, 346, 1147-1168;
65. d) P. Kotrusz, S. Toma, H.-G. Schmalz, A. Adler, Eur. J. Org. Chem. 2004, 1577-1583;
66. e) W. Wang, J. Wang, H. Li, Angew. Chem. 2005, 117, 1393-1395;
67. Angew. Chem. Int. Ed. 2005, 44, 1369-1371;
68. f) Y. Hayashi, H. Gotoh, T. Hayashi, M. Shoji, Angew. Chem. 2005, 117, 4284-4287;
69. Angew. Chem. Int. Ed. 2005, 44, 4212-4215.
70. For a review of asymmetric conjugate additions to nitroalkenes, see: O. M. Berner, L. Tedeschi, D. Enders, Eur. J. Org. Chem. 2002, 1877-1894.
71. a) N. Mase, R. Thayumanavan, F. Tanaka, C. F. Barbas III, Org. Lett. 2004, 6, 2527-2530;
72. b) N. Mase, K. Watanabe, H. Yoda, K. Tanabe, F. Tanaka, C. F. Barbas III, J. Am. Chem. Soc. 2006, 128, 4966-4967.
73. Secondary enamines conjugated to aromatic systems are known to display low reactivity (see Ref. [9]). Relative to nitrostyrene derivatives, inferior product yields have been reported in additions of aldehydes to β-alkyl-substituted nitroalkenes (see Refs. [11a,c-e]).
74. Direct Michael additions to nitroalkenes promoted by secondary amine catalysts typically require large (e.g. tenfold) excess of aldehyde due to competing aldol pathways (see Ref. [11]).
75. 2-Phenylpropionaldehyde was recovered in 2.5% ee, thus indicating that a simple kinetic resolution mechanism is not operative.
76. The addition of 2-methylvaleraldehyde to trans-β-nitrostyrene catalyzed by 20 mol% 3 proceeded with less than 10% conversion.
77. The benefit of added water has been observed in other primary amine catalyzed transformations (see references [2c-j, 8a]).
78. For the conjugate addition of α-amino acid esters to trans-3,3,3-trifluoro-1-nitropropene, see: M. Molteni, A. Volonterio, M. Zanda, Org. Lett. 2003, 5, 3887-3890.
79. The addition of amines to nitroalkenes has been extensively studied with very few stable adducts isolated. Anilines and electron-deficient nitroalkenes lead to relatively stable adducts. For representative studies, see: a) D. E. Worrall, J. Am. Chem. Soc. 1927, 49, 1598-1605;
80. b) R. L. Heath, J. D. Rose, J. Chem. Soc. 1947, 1486-1489;
81. c) F. Brower, H. Burkett, J. Am. Chem. Soc. 1953, 75, 1082-1084;
82. d) J. C. Sowden, A. Kirkland, K. O. Lloyd, J. Org. Chem. 1963, 28, 3516-3518;
83. e) É. S. Lipina, Z. F. Pavlova, T. Y. Paperno, V. V. Perekalin, L. V. Prikhod'ko, Zh. Org. Khim. 1970, 6, 1123-1129.
84. Diastereomers are assumed to arise from competitive reaction of E and Z enamines rather than poor nitroalkene facial selectivity. Consistent with this notion, catalyst 1 promotes the reaction of nitrostyrene with isobutyraldehyde in 99% ee (see Supporting Information for details).
85. For a relevant analysis, see: D. A. Yalalov, S. B. Tsogoeva, S. Schmatz, Adv. Synth. Catal. 2006, 348, 826-832.
86. a) K. C. Brannock, A. Bell, R. D. Burpitt, C. A. Kelly, J. Org. Chem. 1964, 29, 801-812;
87. b) M. E. Kuehne, L. Foley, J. Org. Chem. 1965, 30, 4280-4284;
88. c) A. Risaliti, S. Fatutta, M. Forchiassin, E. Valentin, Tetrahedron Lett. 1966, 7, 1821-1825;
89. d) A. Risaliti, M. Forchiassin, E. Valentin, Tetrahedron Lett. 1966, 7, 6331-6335;
90. e) A. T. Nielsen, T. G. Archibald, Tetrahedron 1970, 26, 3475-3485;
91. f) D. Seebach, J. Golinski, Helv. Chim. Acta 1981, 64, 1413-1423;
92. g) S. J. Blarer, W. B. Schweizer, D. Seebach, Helv. Chim. Acta 1982, 65, 1637-1654;
93. h) S. J. Blarer, D. Seebach, Chem. Ber. 1983, 116, 3086-3096;
94. i) D. Seebach, A. K. Beck, J. Golinski, J. N. Hay, T. Laube, Helv. Chim. Acta 1985, 68, 162-172;
95. j) F. Felluga, P. Nitti, G. Pitacco, E. Valentin, Tetrahedron 1989, 45, 2099-2108;
96. k) F. Felluga, P. Nitti, G. Pitacco, E. Valentin, Tetrahedron 1989, 45, 5667-5678;
97. l) F. Felluga, P. Nitti, G. Pitacco, E. Valentin, J. Chem. Soc. Perkin Trans. 1 1992, 2331-2335.
98. See Supporting Information for experimental evidence for the formation of G.
99. For a discussion of dual activation within the context of asymmetric catalysis by chiral hydrogen-bond donors, see Ref. [6b].
100. Yields are of isolated products after column chromatography. Diastereomeric ratios and enantiomeric excesses were determined by SFC or HPLC analysis compared with authentic racemic material. The absolute configuration of 22 was determined by X-ray crystallography, whereas those of 6-21 were inferred.