Mechanistic investigation of the 2,5-diphenylpyrrolidine-catalyzed enantioselective α-chlorination of aldehydes

Chemistry - A European Journal

Volumn 11, Issue 23, 2005, Pages 7083-7090

  Halland, Nis ^a   Alstrup Lie, Mette ^a   Kjærsgaard, Anne ^a   Marigo, Mauro ^a   Schiøtt, Birgit ^a   Jørgensen, Karl Anker ^a  

^a AARHUS UNIVERSITY   (Denmark)

Author keywords

Asymmetric catalysis; Chlorination; Density functional calculations; Isotope effects; Kinetics; Sigmatropic rearrangement

Indexed keywords

ASYMMETRIC CATALYSIS; DENSITY FUNCTIONAL CALCULATIONS; ISOTOPE EFFECTS; KINETICS; SIGMATROPIC REARRANGEMENTS;

ALDEHYDES; ATOMS; CARBON; CATALYSIS; COMPUTATIONAL METHODS;

AMINES;

2,5 DIPHENYLPYRROLIDINE; 2,5-DIPHENYLPYRROLIDINE; ALDEHYDE; CHLORINE; PYRROLIDINE DERIVATIVE;

CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; CONFERENCE PAPER; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; STEREOISOMERISM;

ALDEHYDES; CATALYSIS; CHLORINE; MAGNETIC RESONANCE SPECTROSCOPY; MODELS, MOLECULAR; PYRROLIDINES; STEREOISOMERISM;

EID: 27944469988     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200500776     Document Type: Conference Paper

References (91)

1. For recent general reviews on organocatalysis see, for example: a) P. I. Dalko, L. Moisan, Angew. Chem. 2004, 116, 5248;
2. Angew. Chem. Int. Ed 2004, 43, 5138;
3. h) J. Seayad. B. List, Org. Biomol. Chem. 2005, 3, 719;
4. c) A. Berkessel, H. Gröger, Metal-Free Organic Catalysts in Asymmetric Synthesis, Wiley-VCH, Weinheim, 2004.
5. See, for example: a) B. List, R. A. Lerner, C. F. Barbas, III, J. Am. Chem. Soc. 2000, 122, 2395;
6. b) A. B. Northrup. I. K. Mangion, F. Hettche, D. W. C. MacMillan, Angew. Chem. 2004, 116, 2204;
7. Angew. Chem. Int. Ed. 2004, 43, 2152;
8. c) B. Alcaide. P. L. Almendros, Angew. Chem. 2004, 116, 884;
9. Angew. Chem. Int. Ed. 2003, 42, 858;
10. d) J. Casas. M. Engquist, I. Ibrahem, B. Kaynak, A. Córdova, Angew. Chem. 2005, 117, 1367;
11. Angew. Chem. Int. Ed. 2005, 44, 1343.
12. See, for example: a) B. List. P. Pojarliev. W. T. Biller, H. J. Martin. J. Am. Chem. Soc. 2002, 124, 827:
13. b) W. Notz. F. Tanaka, S.-i. Watanabe, N. S. Chowdari, J. M. Turner, R. Thayumanavan, C. F. Barbas. III, J. Org. Chem. 2003, 68, 9624:
14. c) A. Córdova, Chem. Eur. J. 2004, 10, 1987.
15. a) A. Boøgevig, K. Juhl, N. Kumaragurubaran, W. Zhuang, K. A. Jørgensen, Angew. Chem. 2002, 114, 1868;
16. Angew. Chem. Int. Ed. 2002, 41, 1790;
17. b) B. List, J. Am. Chem. Soc. 2002, 124, 5656:
18. c) N. Kumaragurubaran, K. Juhl. W. Zhuang, A. Bøgevig, K. A. Jørgensen, J. Am. Chem. Soc. 2002, 124, 6254;
19. d) R. O. Duthaler. Angew. Chem. 2003, 115, 1005;
20. Angew. Chem. Int. Ed. 2003, 42, 975.
21. a) G. Zhong, Angew. Chem. 2003, 115, 4379;
22. Angew. Chem. Int. Ed. 2003, 42, 4247;
23. b) S. P. Brown, M. P. Brochu, C. J. Sinz, D. W. C. MacMillan, J. Am. Chem. Soc. 2003, 125, 10808;
24. c) A. Bøgevig, H. Sundéen. A. Córdova, Angew. Chem. 2004, 116, 1129:
25. Angew. Chem. Int. Ed. 2004, 43, 1109;
26. d) M. Hayashi, J. Yamaguchi, T. Sumiya, M. Shoji, Angew. Chem. 2003, 115, 1132;
27. Angew. Chem. Int. Ed. 2004, 43, 1112.
28. M. Mauro, T. Wabnitz, D. Fielenbach, K. A. Jørgensen, Angew. Chem. 2005, 117, 804;
29. Angew. Chem. Int. Ed. 2005, 44, 794.
30. a) M. Marigo, D. Fielenbach, A. Braunton, A. Kjærsgaard, K. A. Jørgensen, Angew. Chem. 2005, 117, 3769;
31. Angew. Chem. Int. Ed. 2005, 44, 3703;
32. b) D. D. Steiner, N. Mase, C. F. Barbas, III, Angew. Chem. 2005, 117, 3772;
33. Angew. Chem. Int. Ed. 2005, 44, 3706;
34. c) T. D. Beeson, D. W. C. MacMillan, J. Am. Chem. Soc. 2005, 127, 8826;
35. d) D. Enders, R. M. Hüttl, Synlett 2005, 991.
36. a) M. P. Brochu, S. P. Brown, D. W. C. MacMillan, J. Am. Chem. Soc. 2004, 126, 4108;
37. b) N. Halland, A. Braunton, S. Bachmann, M. Marigo, K. A. Jørgensen, J. Am. Chem. Soc. 2004, 126, 4790.
38. M. Marigo, S. Bachmann, N. Halland, A. Braunton, K. A. Jørgensen, Angew. Chem. 2004, 116, 5623;
39. Angew. Chem. Int. Ed. 2004, 43, 5507.
40. a) L. Hintermann, A. Togni, Angew. Chem. 2000, 112, 4530;
41. Angew. Chem. Int. Ed. 2000, 39, 4359;
42. b) L. Hintermann, A. Togni, Helv. Chim. Acta. 2000, 83, 2425;
43. c) H. Ibrahim, F. Kleinbeck, A. Togni, Helv. Chim. Acta. 2004, 87, 605;
44. d) Y. Hamashima, K. Yaga, H. Takano, L. Tomás, M. Sodeoka, J. Am. Chem.Soc. 2002, 124, 14530;
45. e) J.-A. Ma, D. Cahard, Tetrahedon: Asymmetry 2004, 15, 1007;
46. f) M. Marigo, N. Kumaragurubaran, K. A. Jørgensen, Chem. Eur. J. 2004, 10, 2133;
47. g) L. Bernardi, K. A. Jørgensen, Chem. Commun. 2005, 1324;
48. h) Y. Hamashima, T. Suzuki, Y. Shimura, T. Himizu, N. Umebayashi, T. Tamura, N. Sasamoto, M. Sodeoka, Tetrahedron Lett. 2005, 46, 1447;
49. i) N. Shibata, J. Kohno, K. Takai, T. Ishimura, S. Nakamura, T. Toru, S. Kanamasa, Angew. Chem. 2005, 117, 4276;
50. Angew. Chem. Int. Ed. 2005, 44, 4204;
51. j) Y. Hamashima, T. Suzuki, H. Takano, Y. Shimura, M. Sodeoka, J. Am. Chem.Soc. 2005, 127, 10164.
52. a) H. Wack, A. E. Taggi, A. M. Hafez, W. J. Drury III, T. Lectka, J. Am. Chem. Soc. 2001, 123, 1531;
53. b) S. France, H. Wack, A. E. Taggi, A. M. Hafez, T. R. Wagerle, M. H. Shah, C. L. Dusich, T. Lectka, J. Am. Chem. Soc. 2004, 126, 4245.
54. For recent reviews on α-halogenation of carbonyl compounds see: a) H. Ibrahim, A. Togni, A. Chem. Commun. 2004, 1147;
55. b) K. Muniz, Angew. Chem. 2001, 113, 1701;
56. Angew. Chem. Int. Ed. 2001, 40, 1653;
57. c) M. Oestreich, Angew. Chem. 2005, 117, 2376;
58. Angew. Chem. Int. Ed. 2005, 44, 2324;
59. d) S. France, A. Weatherwax, T. Lectka, Eur. J. Org. Chem. 2005, 475.
60. a) J. March, Advanced Organic Chemistry: Reactions, Mechanisms and Structure, 4th ed., Wiley, New York, 1992;
61. b) N. De Kimpe, R. Verhé, The Chemistry of α-Haloketones, α-Haloaldehydes, and α-Haloimines, Wiley, New York, 1990;
62. c) For a recent example of alkylation of α-chloroketones without loss of optical purity; see, for example:
63. d) C. F. Malosh, J. M. Ready, J. Am. Chem. Soc. 2004, 126, 10240.
64. [18] at the B3LYP/6-31G(d) level of theory.
65. a) R. B. Woodward, R. Hoffmann, J. Am. Chem. Soc. 1965, 87, 2511;
66. b) R. B. Woodward, R. Hoffmann, Angew. Chem. 1969, 57, 797;
67. Angew. Chem. Int. Ed. Engl. 1969, 8, 781.
68. a) M. De Rosa, J. L. T. Alonso, J. Org. Chem. 1978, 43, 2639;
69. b) M. De Rosa, L. Carbognani, A. J. Febres, Org. Chem. 1981, 46, 2054; a 1,3-sigmatropic shift of a nosyloxy group has also been suggested as the mechanism for the nosyloxylation of enamines, see
70. c) R. V. Hoffman, S. Carr, B. C. Jankowski, J. Org. Chem. 1985, 50, 5148.
71. See, for example: a) C. Allemann, R. Gordillo, F. R. Clemente, P. H.-Y. Cheong, K. N. Houk, Acc. Chem. Res. 2004, 37, 558;
72. b) L. Hoang, B. Bahmanyar, K. N. Houk, B. List, J. Am. Chem. Soc. 2003, 125, 16;
73. c) P. H.-Y. Cheong, K. N. Houk, J. Am. Chem. Soc. 2004, 126, 13912;
74. d) F. R. Clemente, K. N. Houk, Angew. Chem. 2004, 116, 5890;
75. Angew. Chem. Int. Ed. 2004, 43, 5766.
76. a) Gaussian 98, Revision A.7, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R.E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh PA, 1998;
77. b) Gaussian 03. Revision B.05, M. J. Frisch, G.W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian, Inc., Pittsburgh PA, 2003.
78. T. H. Lowry, K. S. Richardson, Mechanism and Theory in Organic Chemistry, 3rd ed., Harper Collins, New York, 1987.
79. See, for example: C. Girand, H. B. Kagan, Angew. Chem. 1998, 110. 3088;
80. Angew. Chem. Int. Ed. 1998, 37, 2922.
81. This behaviour is not unusual in catalytic reactions as the concentration of the catalyst is usually much lower than that of the reactants.
82. 1H NMR spectroscopy and GC. In all cases, the optical purity of the α-chlorobutanal formed in the reaction remained a constant 95 % ee throughout the reaction.
83. 2.
84. P. Seguineau, J. Vilieras, Tetrahedron Lett. 1988, 29, 477.
85. a) C. Peng, P. Y. Ayala, H. B. Schlegel, M. J. Frisch, J. Comp. Chem. 1996, 17, 49;
86. b) C. Peng, H. B. Schlegel, Isr. J. Chem. 1993, 33, 449.
87. G. Schaftenaar, J. H. Noordik, J. Comput.-Aided Mol. Des. 2000, 14, 123.
88. a) C. Gonzalez, H. B. Schlegel, J. Chem. Phys. 1989, 90, 2154;
89. b) C. Gonzalez, H. B. Schlegel, J. Phys. Chem. 1990, 94, 5523.
90. a) V. Barone, M. Cossi, J. Phys. Chem. A 1998, 102, 1995;
91. b) M. Cossi, N. Rega, G. Scalmani, V. Barone, J. Comput. Chem. 2003, 24, 669.