Tuning the enantioselective N-acetylation of racemic amines: A spectacular salt effect

Journal of the American Chemical Society

Volumn 127, Issue 17, 2005, Pages 6138-6139

  Arseniyadis, Stellios ^a   Subhash, Pithani V ^a   Valleix, Alain ^b   Mathew, Suju P ^c   Blackmond, Donna G ^c   Wagner, Alain ^a   Mioskowski, Charles ^a,b  

^a UNIVERSITÉ DE STRASBOURG   (France)

^b CEA SACLAY   (France)

^c IMPERIAL COLLEGE LONDON   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE;

ACETYLATION; ARTICLE; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL REACTION KINETICS; ENANTIOSELECTIVITY; RACEMIC MIXTURE;

EID: 18244398432     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja051302+     Document Type: Article

References (19)

1. Pasteur, L. C. R. Hebd. Seance Acad. Sci. Paris 1848, 26, 535.
2. For reviews on kinetic resolution, see: (a) Keith, J. M.; Larrow, J. F.; Jacobsen, E. N. Adv. Synth. Catal. 2001, 1, 5.
3. (b) Hoveyda, A. H.; Didiuk, M. T. Curr. Org. Chem. 1998, 2, 489.
4. (c) Kagan, H. B.; Fiaud, J. C. Top. Stereochem. 1988, 18, 249.
5. For reviews on the kinetic resolution of alcohols, see: (a) Spivey, A. C.; Maddaford, A.; Redgrave, A. Org. Prep. Proc. Int. 2000, 32, 331.
6. (b) France, S.; Guerin, D. J.; Miller, S. J.; Lectka, T. Chem. Rev. 2003, 103, 2985.
7. For a review on methods for the asymmetric synthesis of amines, see: Johansson, A. Contemp. Org. Synth. 1995, 2, 393.
8. For reviews on the use of amines bearing an adjacent enantiomerically pure chiral center in organic chemistry as chiral auxiliaries, resolving agents, and intermediates in the synthesis of biologically important molecules, see: (a) Whitesell, J. K. Chem. Rev. 1989, 89, 1591.
9. (b) Seyden-Penne, J. Chiral Auxiliaries and Ligands in Asymmetric Synthesis; Wiley: New York, 1995, p 306.
10. (c) Jacques, J.; Collet, A.; Wilen, S. H. Enantiomers, Racemates, and Resolution; Wiley: New York, 1981.
11. (d) Moser, H.; Rihs, G.; Senter, H. Z. Naturforsch. 1982, 376.
12. For previous reports on nonenzymatic kinetic resolution of amines, see: (a) Kondo, K.; Kurosaki, T.; Murakami, Y. Synlett 1998, 725.
13. (b) Ie, Y.; Fu, G. C. Chem. Commun. 2000, 119.
14. (c) Arai, S.; Bellemin-Laponnaz, S.; Fu, G. C. Angew. Chem., Int. Ed. 2001, 40, 234.
15. Arseniyadis, S.; Valleix, A.; Wagner, A.; Mioskowski, C. Angew. Chem., Int. Ed. 2004, 43, 3314.
16. With chiral 1 in hand, KR of (±)-1-phenylethylamine was achieved with unprecedented levels of enantioselectivity. Up to 84% ee (s = 30) was obtained at room temperature using 0.5 equiv of reagent and up to 90% ee using 0.33 equiv of reagent at -20 °C.
17. Arseniyadis, S.; Subhash, P. V.; Valleix, A.; Wagner, A.; Mioskowski, C. Submitted.
18. Standard conditions: the enantioselective N-acetylation reactions were performed on (±)-1-phenylethylamine using 0.5 molar equiv of chiral (1S,2S)-1 in THF and at room temperature.
19. Conversion percent determined by GC analysis using an internal standard and by quantifying the isolated acetylated product after flash chromatography.