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Volumn 125, Issue 25, 2003, Pages 7596-7601

New insights in the mechanism of amine catalyzed epoxidation: Dual role of protonated ammonium salts as both phase transfer catalysts and activators of Oxone

Author keywords

[No Author keywords available]

Indexed keywords

CATALYZED EPOXIDATION;

EID: 0038546766     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0289088     Document Type: Article
Times cited : (102)

References (43)
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    • Jacobsen E.N., Pfaltz A., Yamamoto H., Eds.; Springer-Verlag Berlin
    • Jacobsen. E. N.; Wu, M. H. Comprehensive Asymmetric Catalytsis II; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer-Verlag: Berlin. 1999; pp 649-677.
    • (1999) Comprehensive Asymmetric Catalytsis II , pp. 649-677
    • Jacobsen, E.N.1    Wu, M.H.2
  • 3
  • 5
    • 79959372443 scopus 로고    scopus 로고
    • The corrected data for the competition experiments have now been reported. See: Adamo, M. F. A.; Aggarwal, V. K.; Sage, M. A. J. Am. Chem. Soc. 2002, 124, 11223-11223. We have also been unable to reproduce Bauld and Mirafzal radical cation mediated epoxidations described in ref 3.
    • (2002) J. Am. Chem. Soc. , vol.124 , pp. 11223
    • Adamo, M.F.A.1    Aggarwal, V.K.2    Sage, M.A.3
  • 6
    • 0037884934 scopus 로고    scopus 로고
    • note
    • In the original work this was erroneously reported as 57% ee.
  • 8
    • 0037884939 scopus 로고    scopus 로고
    • note
    • (S)-diphenylprolinol 3 was purchased from Aldrich.
  • 17
    • 3342981841 scopus 로고
    • For examples of oxidation of amines with Oxone see: Kennedy, R. J.; Stock, A. M. J. Org. Chem. 1960, 25, 1901-1906.
    • (1960) J. Org. Chem. , vol.25 , pp. 1901-1906
    • Kennedy, R.J.1    Stock, A.M.2
  • 18
    • 0029160418 scopus 로고
    • (a) For examples of oxidation of amines with Oxone/acetone system see: Brik, M. E. Tetrahedron Lett. 1995, 36, 5519-5522.
    • (1995) Tetrahedron Lett. , vol.36 , pp. 5519-5522
    • Brik, M.E.1
  • 22
    • 0001450199 scopus 로고
    • Murahashi, S.-I.; Imada, Y.; Ohtake, H. J. Org. Chem. 1994, 59, 6170-6172. In the case of 3, the mechanism below could account for the formation of benzophenone and nitrone.
    • (1994) J. Org. Chem. , vol.59 , pp. 6170-6172
    • Murahashi, S.-I.1    Imada, Y.2    Ohtake, H.3
  • 23
    • 0037547099 scopus 로고    scopus 로고
    • note
    • 2O.
  • 32
    • 0001349563 scopus 로고
    • Protonated Oxone (i.e. Oxone at low pH) is a powerful electrophilic oxidant. See: Zhu, W.; Ford, W. T. J. Org. Chem. 1991, 56, 7022-7026.
    • (1991) J. Org. Chem. , vol.56 , pp. 7022-7026
    • Zhu, W.1    Ford, W.T.2
  • 39
    • 0038222506 scopus 로고    scopus 로고
    • note
    • 2O (Table 3, entry 5).
  • 40
    • 0001474702 scopus 로고
    • There are examples of protonated ammonium salts directing epoxidation through hydrogen bonding with the oxidant (m-CPBA or dimethyloxirane) whilst quaternary ammonium salts gave opposite selectivity. See: (a) Asensio, G.; González-Núñez, M. E.; Boix-Benardini, C.; Mello, R.; Adam, W. J. Am. Chem. Soc. 1993, 115, 7250-7253.
    • (1993) J. Am. Chem. Soc. , vol.115 , pp. 7250-7253
    • Asensio, G.1    González-Núñez, M.E.2    Boix-Benardini, C.3    Mello, R.4    Adam, W.5
  • 41
    • 0033603592 scopus 로고    scopus 로고
    • (b) Asensio. G.; Boix-Benardini, C.; Andreu. C.; González-Núñez, M. E.; Mello, R.; Edwards, J. O.; Carpenter, G. B. J. Org. Chem. 1999, 64, 4705-4711. These reactions are analogous to the seminal work of Henbest27 on hydroxy-directed epoxidations but do not relate to phase transfer catalysed epoxidations of the type described in this paper. Nevertheless, we appreciate one of the reviewers directing us to this work.
    • (1999) J. Org. Chem. , vol.64 , pp. 4705-4711
    • Asensio, G.1    Boix-Benardini, C.2    Andreu, C.3    González-Núñez, M.E.4    Mello, R.5    Edwards, J.O.6    Carpenter, G.B.7


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.