Highly regioselective and diastereoselective epoxidation of allylic amines with Oxone

Chemical Communications

Volumn , Issue 27, 2005, Pages 3448-3450

  Aggarwal, Varinder K ^a   Fang, Guang Yu ^a  

^a UNIVERSITY OF BRISTOL   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL COMPOUND; AMINE; AMMONIA; SODIUM PEROXIDE;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; COMPLEX FORMATION; EPOXIDATION; HYDROGEN BOND; OXIDATION; PROTON TRANSPORT; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 23044495239     PISSN: 13597345     EISSN: None     Source Type: Journal    
DOI: 10.1039/b503516c     Document Type: Article

References (17)

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10. For a recent example of diastereoselective, amide-directed epoxidation see: P. O'Brien, A. C. Childs, G. J. Ensor, C. L. Hill, J. P. Kirby, M. J. Dearden, S. J. Oxenford and C. M. Rosser, Org. Lett., 2003, 5, 4955 and references therein.
11. For examples of ketone directed epoxidation see: A. Armstrong, P. A. Barsanti, P. A. Clarke and A. Wood, J. Chem. Soc., Perkin Trans. 1, 1996, 1373.
12. For hydroxy-directed epoxidation using sulfonic peracids see: R. Kluge, M. Schulz and S. Liebsch, Tetrahedron, 1996, 52, 2957.
13. H. B. Henbest and R. A. L. Wilson, J. Chem. Soc., 1959, 1958;
14. H. B. Henbest, Proc. Chem. Soc., 1963, 159.
15. The ammonium salts 1 and 4 were made from 2-cyclohexen-1-one (Scheme 5). Experimental details and related analytical data are included in the Electronic Supplementary Information.
16. Geraniol has often been employed to examine the power of hydroxy-promoted epoxidation. The remote 6,7-alkene is more electron rich than the 2,3-alkene and the ratio of regioisomeric products gives a measure of the relative rates of epoxidation. See: W. Adam and A. K. Smerz, Bull. Soc. Chim. Belg., 1996, 105, 581.
17. According to the proposed mechanism for the epoxidation of protonated allylic amines with m-CPBA (see ref. 4 and 5), the hydrogen bonding interaction between m-CPBA and protonated amino group should also enhance its reactivity.