Origins of selectivities in proline-catalyzed α-aminoxylations

Journal of the American Chemical Society

Volumn 126, Issue 43, 2004, Pages 13912-13913

  Cheong, Paul Ha Yeon ^a   Houk, K N ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDE; KETONE; PROLINE;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; OXIDATION; QUANTUM MECHANICS; STEREOCHEMISTRY;

ALDEHYDES; CATALYSIS; DIMERIZATION; MODELS, MOLECULAR; NITROSO COMPOUNDS; PROLINE; QUANTUM THEORY; THERMODYNAMICS;

EID: 7444257444     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0464746     Document Type: Article

References (36)

1. (a) Brown, S. P.; Brochu, M. P.; Sinz, C. J.; MacMillan D. W. C. J. Am. Chem. Soc. 2003, 125, 10808.
2. (b) Zhong, G. Angew. Chem., Int. Ed. 2003, 42, 4247.
3. (c) Hayashi, Y.; Yamaguchi, J.; Hibino, K.; Shoji, M. Tetrahedron Lett. 2003, 44, 8293.
4. (d) Zhong, G.; Yu, Y. Org. Lett. 2004, 6, 1637.
5. (a) Hayashi, Y.; Yamaguchi, J.; Sumiya, T.; Shoji, M. Angew. Chem., Int. Ed. 2004, 43, 1112.
6. (b) Bøgevig, A.; Sundén, H.; Córdova, A. Angew. Chem., Int. Ed. 2004, 43, 1109.
7. (c) Tetrazole derivative of proline has also shown to catalyze the α-aminoxylation, while the reaction of nitrosobenzene with pyrrolidine enamines results in α-hydroxyamination. Momiyama, N.; Torii, H.; Saito, S.; Yamamoto, H. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 5374.
8. (d) Córdova, A.; Sundén, H.; Bøgevig, A.; Johansson, M.; Himo, F. Chem. Eur. J. 2004, 10, 3673.
9. (a) Morikawa, K.; Park, J.; Andersson, P. G.; Hashiyama, T.; Sharpless, K. B. J. Am. Chem. Soc. 1993, 115, 8463.
10. (b) Hashiyama, T.; Morikawa, K.; Sharpless, K. B. J. Org. Chem. 1992, 57, 5067.
11. (c) Zhu, Y.; Yu, Y.; Yu, H.; Shi, Y. Tetrahedron Lett. 1998, 39, 7819.
12. (d) Adam, W.; Fell, R. T.; Saha-Moller, C. R.; Zhao, C.-G. Tetrahedron: Asymmetry 1998, 9, 397.
13. (e) Fukuda, T.; Katsuki, T. Tetrahedron Lett. 1996, 37, 4389.
14. (f) Adam, W.; Fell, R. T.; Stegmann, V. R.; Saha-Moller, C. R. J. Am. Chem. Soc. 1998, 120, 708.
15. (g) Momiyama, N.; Yamamoto, H. J. Am. Chem. Soc. 2003, 125, 6038.
16. (h) Momiyama, N.; Yamamoto, H. Angew. Chem., Int. Ed. 2002, 41, 2986.
17. (i) Momiyama, N.; Yamamoto, H. Org. Lett. 2002, 4, 3579.
18. (j) Yamamoto, Y.; Yamamoto, H. J. Am. Chem. Soc. 2004, 126, 4128.
19. (k) Yamamoto, Y.; Momiyama, N.; Yamamoto, H. J. Am. Chem. Soc. 2004, 126, 5962.
20. Leach, A. G.; Houk, K. N. J. Am. Chem. Soc. 2002, 124, 14820.
21. Blackmond has discovered that aminoxylation reactions manifest an accelerating reaction rate and has proposed a more complex mechanism involving the initial reaction product. This proposal is the subject of current investigations. Mathew, S. P.; Iwamura, H.; Blackmond, D. G. Angew. Chem., Int. Ed. 2004, 43, 3317.
22. Allemann, C.; Gordillo, R.; Cheong, P. H.-Y.; Houk, K. N. Acc. Chem. Res. 2004, 37, 558.
23. Bahmanyar, S.; Houk, K. N. Org. Lett. 2003, 5, 1249-1251.
24. (a) Nakamoto, K.; Rundle, R. E. J. Am. Chem. Soc. 1956, 78, 1114.
25. (b) Holmes, R. R. J. Org. Chem. 1964, 29, 3077.
26. (c) Holmes, R. R.; Bayer, R. P.; Nicholas, D. L. J. Org. Chem. 1967, 32, 2912.
27. In the Lewis acid-catalyzed enol ether-mediated aminoxylation, Yamamoto states that the presence of Lewis acids promote the dimerization of nitrosobenzene and forces the nucleophilic attack to occur on the oxygen of the nitrosobenzene dimer. See ref 3h.
28. (a) The stationary points (reactants and transition structures) were optimized and characterized by frequency analysis using hybrid density functional theory (B3LYP) and the 6-31G(d) basis set as implemented in the Gaussian 98 and 03 series of programs (see Supporting Information for a complete list of authors of these programs).
29. (b) Solvation free energies were calculated for DMSO with the PCM solvation model and UAKS radii using the HF/6-31+G(d, p) level of theory, as implemented in Gaussian 03.
30. (c) Transition state theory was used to predict the stereoselectivity.
31. Bahmanyar, S.; Houk, K. N. J. Am. Chem. Soc. 2001, 123, 12911-12912.
32. (a) See ref 6.
33. (b) Clemente, F.; Allemann, C.; Houk, K. N. Manuscript in preparation.
34. (c) Arnó, M.; Zaragozá, R. J.; Domingo, L. R. Tetrahedron Asymmetry 2004, 15, 1541.
35. Figures prepared with Houkmol, version 2.6.3; Nakamura, K.; Houk, K. N. NAIST: UCLA, 2004.
36. Energies presented in the text are the sums of Gibbs free energy and solvation energy.