Enhancing the Catalytic Activity of 4-(Dialkylamino)pyridines by Conformational Fixation

Angewandte Chemie - International Edition

Volumn 42, Issue 39, 2003, Pages 4826-4828

  Heinrich, Markus R ^a   Klisa, Heike Sabine ^a   Mayr, Herbert ^a   Steglich, Wolfgang ^a   Zipse, Hendrik ^a  

^a UNIVERSITY OF MUNICH   (Germany)

Author keywords

Ab initio calculations; Acylation; Dimethylaminopyridine; Kinetics

Indexed keywords

ACETYLATION; ALCOHOLS; CATALYST ACTIVITY; CONFORMATIONS;

TERTIARY ALCOHOLS;

AROMATIC COMPOUNDS;

ALKYL GROUP; PYRIDINE DERIVATIVE;

ACETYLATION; ACYLATION; ARTICLE; CATALYSIS; CATALYST; CONFORMATION; ENTHALPY; MOLECULAR STABILITY; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS;

EID: 0142214745     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200352289     Document Type: Article

References (38)

1. a) W. Steglich, G. Höfle, Angew. Chem. 1969, 81, 1001; Angew. Chem. Int. Ed. Engl. 1969, 8, 981;
2. a) W. Steglich, G. Höfle, Angew. Chem. 1969, 81, 1001; Angew. Chem. Int. Ed. Engl. 1969, 8, 981;
3. b) G. Höfle, W. Steglich, Synthesis 1972, 619-621.
4. For kinetic evidence for the high catalytic activity of DMAP in the benzoylation of aryl amines, see: L. M. Litvinenko, A. I. Kirichenko, Dokl. Akad. Nauk SSSR Ser. Khim. 1967, 176, 97-100.
5. For reviews, see: a) G. Höfle, W. Steglich, H. Vorbrüggen, Angew. Chem. 1978, 90, 602-615; Angew. Chem. Int. Ed. Engl. 1978, 17, 569-583;
6. For reviews, see: a) G. Höfle, W. Steglich, H. Vorbrüggen, Angew. Chem. 1978, 90, 602-615; Angew. Chem. Int. Ed. Engl. 1978, 17, 569-583;
7. b) E. F. V. Scriven, Chem. Soc. Rev. 1983, 12, 129-161;
8. c) A. Hassner in Encyclopedia of Reagents for Organic Synthesis, Vol. 3 (Ed.: L. A. Paquette), Wiley, Chichester, 1995, pp. 2022-2024.
9. a) B. Neises, W. Steglich, Angew. Chem. 1978, 90, 556-557; Angew. Chem. Int. Ed. Engl. 1978, 17, 552;
10. a) B. Neises, W. Steglich, Angew. Chem. 1978, 90, 556-557; Angew. Chem. Int. Ed. Engl. 1978, 17, 552;
11. b) A. Hassner, V. Alexanian, Tetrahedron Lett. 1978, 4475-4478.
12. a) J. Inanaga, K. Hirata, H. Saeki, T. Katsuki, M. Yamaguchi, Bull. Chem. Soc. Jpn. 1979, 52, 1989-1993;
13. b) E. P. Boden, G. E. Keck, J. Org. Chem. 1985, 50, 2394-2395.
14. S. K. Chaudhary, O. Hernandez, Tetrahedron Lett. 1979, 99-102.
15. a) E. Vedejs, X. Chen, J. Am. Chem. Soc. 1996, 118, 1809-1810;
16. b) J. C. Ruble, G. C. Fu, J. Org. Chem. 1996, 61, 7230-7231;
17. c) T. Kawabata, M. Nagato, K. Takasu, K. Fuji, J. Am. Chem. Soc. 1997, 119, 3169-3170;
18. d) B. Tao, J. C. Ruble, D. A. Hoic, G. C. Fu, J. Am. Chem. Soc 1999, 121, 5091-5092;
19. e) A. C. Spivey, T. Fekner, S. E. Spey, H. Adams, J. Org. Chem. 1999, 64, 9430-9443, and references therein;
20. f) A. C. Spivey, T Fekner, S. E. Spey, J. Org. Chem. 2000, 65, 3154-3159;
21. g) A. C. Spivey, A. Maddaford, T. Fekner, A. J. Redgrave, C. S. Frampton, J. Chem. Soc. Perkin Trans. 1 2000, 3460-3468;
22. h) G. C. Fu, Acc. Chem. Res. 2000, 33, 412-420, and references therein;
23. i) A. C. Spivey, A. Maddaford, T. Fekncr, D. P. Leese, A. J. Redgrave, C. S. Frampton, J. Chem. Soc. Perkin Trans. 1 2001, 1785-1794;
24. j) G. Priem, B. Pelotier, S. J. F. Macdonald, M. S. Anson, I. B. Campbell, J. Org. Chem. 2003, 68, 3844-3848;
25. k) S. France, D. J. Guerin, S. J. Miller, T. Lectka, Chem. Rev. 2003, 103, 2985-3012.
26. W. Steglich, G. Höfle, Tetrahedron Lett. 1970, 54, 4727-4730.
27. A. Hassner, L. R. Krepski, V. Alexanian, Tetrahedron 1978, 34, 2069-2076.
28. Compare the analogous effects in the enamine series: a) S. Hünig, H. Hoch, Fortschr. Chem. Forsch. 1970, 14, 235-293;
29. b) B. Kempf, N. Hampel, A. R. Ofial, H. Mayr, Chem. Eur. J. 2003, 9, 2209-2218.
30. a) H. Mayr, T. Bug, M. F. Gotta, N. Hering, B. Irrgang, B. Janker, B. Kempf, R. Loos, A. R. Ofial, G. Remennikov, H. Schimmel, J. Am. Chem. Soc. 2001, 123, 9500-9512;
31. b) H. Mayr, B. Kempf, A. R. Ofial, Acc. Chem. Res. 2003, 36, 66-77.
32. [17] Energy data and structural parameters for pyridine, the pyridine bases 1, 2, 6, and 7, and their N-acetyl derivatives are given in the Supporting Information.
33. a) K. Tsuda, S. Saeki, S. Imura, S. Okuda, Y. Sato, H. Mishima, J. Org. Chem. 1956, 21, 1481-1486;
34. b) T. Sakomoto, N. Miura, Y. Kondo, H. Yamanaka, Chem. Pharm. Bull. 1986, 34, 2018-2023.
35. J. N. Reed, J. Rotchford, D. Strickland, Tetrahedron Lett. 1988, 29, 5725-5728.
36. The synthesis of 6 and the spectroscopic data of compounds 6 and 7 are described in the Supporting Information.
37. The importance of the auxiliary base is illustrated by the fact that the half-life for the acetylation of 8 under the catalysis of 7 is increased from 151 to 465 min if pyridine is used instead of triethylamine.
38. 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, 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, 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. G. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1998.