Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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A Direct Comparison Study of Asymmetric Borane Reduction of C=N Double Bond Mediated by Chiral Oxazaborolidines

  • Cho Byung Tae (Department of Chemistry, Hallym University) ;
  • Ryu, Mi Hae (Department of Chemistry, Hallym University) ;
  • Chun Yu Sung (Department of Chemistry, Hallym University) ;
  • Dauelsberg Ch. (Fachbereich Chemie, Universit$\"{a}$t Oldenburg) ;
  • Wallbaum Sabine (Fachbereich Chemie, Universit$\"{a}$t Oldenburg) ;
  • Martens Jurgen (Fachbereich Chemie, Universit$\"{a}$t Oldenburg)
  • Published : 1994.01.20
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Abstract

A comparison study on asymmetric borane reduction of ketoxime ethers and N-substituted ketimines possesing C = N double bond mediated by the selected chiral oxazaborolidines (1-6) was investigated. Thus, an aromatic ketoxime O-alkyl ether acetophenone oxime O-methyl ether was reduced to the corresponding amine (1-phenylethylamine 8a) with optical yields, such as 58% ee with 1, 86% ee with 2, 3% ee with 3, 99% ee with 4, 60% ee with 5, and 73% ee with 6. However, the reduction of an aliphatic ketoxime derivative 2-heptanone oxime O-methyl ether provided low optical inductions (7-13% ee). For ketoxime O-trimethylsilyl ethers, the reduction of acetophenone O-trimethylsilyl ether afforded 8a with optical yields which were 90% ee with 1, 40% ee with 2, 2% ee with 3, 62% ee with 4, 5% ee with 5, and 60% ee with 6. The reduction of 2-heptanone O-trimethylsilyl ether also gave the product amine with low optical yields (10-40% ee). In the case of N-substituted ketimines, the reduction of acetophenone N-phenylimine afforded the corresponding amine with 79% ee, 78% ee, 9% ee, 73% ee, 78% ee and 67% ee using 1, 2, 3, 4, 5, and 6, respectively, whereas low optical inductions (5-18% ee) for 2-heptanone N-phenylimine were achieved.

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References

  1. J. Chem. Soc. Perkin Trans. I Cho, B. T.;Cho, Y. S.
  2. Tetrahedron: Asymmetry v.3 Cho, B. T.;Chun, Y. S.
  3. Synthesis Singh, V. K.
  4. Tetrahedron: Asymmetry v.3 Wallbum, S.;Martens, J.
  5. Chem. Rev. v.93 Deloux, A.;Srebnik, M.
  6. Tetrahedron: Asymmetry v.3 Cho, B. T.;Chun, Y. S.
  7. J. Am. Chem. Soc. v.109 Corey, E. J.;Bakshi, R. K.;Shibata, S.
  8. Tetrahedron: Asymmetry v.2 Wallbaum. S.;Martens, J.
  9. Synth. Commun. v.22 Behnen, W.;Ch, Dauelsberg, Wallbaum, S.;Martens, J.
  10. Tetrahedron v.23 Karabatsos, G. J.;Hsi, N.
  11. Chem. Ber. v.113 Knorr, R.;Weiss, A.;Low, P.;Papple, E.
  12. J. Org. Chem. v.41 Montgomery, F. C.;Saunders, Jr., W. H.
  13. Chem. Ber. v.113 Knorr, R.
  14. J. Am. Chem. Soc. v.105 Smith, J. K.;Bergbreiter, D. E.;Newcomb, M.
  15. J. Org. Chem. v.38 Guthrie, R. D.;Burdon, L. G.;Lovell, Jr. F. L.
  16. J. Am. Chem. Soc. v.108 Brown, H. C.;Kim, K-W.;Cole, T. E.;Singaram, B.
  17. Organic Synthesis via Organoboranes Brown, H. C.;Kramer, G. W.;Levy, A. B.;Midland, M. M.
  18. J. Chem. Soc. C. Grundon, M. F.;Khan, W. A.;Boyd, D. R.;Jackson, W. R.
  19. J. Chem. Soc., Perkin Trans. I Yamada, M.;Takeda, M.;Iwakuma, T.
  20. J. Chem. Soc., Perkin Trans. I Landor, S. R.;Sonola, O. O.;Tatchel, A. R.
  21. J. Org. Chem. v.52 Hutchins, R. O.;Abdel-Magid, A.;Sterecho, Y. P.;Ambsgan, A.
  22. Tetrahedron: Asymmetry v.3 Kawate, T.;Nakagawa. M.;Kakikawa, T.;Hino, T.
  23. J. Chem. Soc., Perkin Trans. I Itsuno, S.;Nakano, M.;Miyazaki, K.;Masuda, H.;Ito, K.;Hirao, A.;Nakahama, S.
  24. J. Chem. Soc., Perkin Trans. I Itsuno, S.;Nakano, M.;Ito, K.;Hirao, A.;Owa, M.;Kanda, N.;Nakahama, S.
  25. Polymer v.28 Itsuno, S.;Ito, Y.K.;Hirao, A.;Nakahama, S.
  26. Bull. Chem. Soc. Jpn. v.60 Itsuno, S.;Sakurai, Y.;Ito, K.;Nakahama, S.
  27. J. Chem. Soc., Perkin Trans. I Itsuno, S.;Sakurai, Y.;Shimizu, K.;Ito, K.
  28. J. Chem. Soc., Perkin Trans. I Itsuno, S.;Sakurai, Y.;Shimizu, K.;Ito, K.

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