Chemoselective allylation of aldimine with allyltriethylgermane by the combined use of BF3•OEt2 and AcOH

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Takahiko Akiyama, Junko Iwai, Yuji Onuma and Hirotaka Kagoshima


Abstract

Allyltriethylgermane reacts with aldimines in preference to aldehydes by means of BF3•OEt2 and AcOH to afford homoallylic amines in high yields; three component syntheses of homoallytic amines starting from aldehyde, aniline and allylgermane were successfully achieved.


References

  1. E. F. Kleinman and R. A. Volkmann, in Comprehensive Organic Synthesis, ed. B. M. Trost and I. Fleming, Pergamon, Oxford, 1991, vol. 2, p. 975 Search PubMed; Y. Yamamoto and N. Asao, Chem. Rev., 1993, 93, 2207 Search PubMed.
  2. R. A. Volkmann, in Comprehensive Organic Synthesis, ed. B. M. Trost and I. Fleming, Pergamon, Oxford, 1991, vol. 1, p. 355 Search PubMed; R. Bloch, Chem. Rev., 1998, 98, 1407 Search PubMed.
  3. Although Grieco and co-workers reported three allylations of aldimines generated in situ from aldehyde, only formaldehyde was employed. See: S. D. Larsen, P. A. Grieco and W. F. Fobare, J. Am. Chem. Soc., 1986, 108, 3512 Search PubMed; P. A. Grieco and A. Bahsas, J. Org. Chem., 1987, 52, 1378 CrossRef CAS.
  4. H. Nakamura, N. Asao and Y. Yamamoto, J. Chem. Soc., Chem. Commun., 1995, 1273 RSC; H. Nakamura, H. Iwama and Y. Yamamoto, J. Am. Chem. Soc., 1996, 118, 6641 CrossRef CAS.
  5. S. Kobayashi, Synlett, 1994, 689 CrossRef CAS; S. Kobayashi, Eur. J. Org. Chem., 1999, 15 CrossRef CAS.
  6. S. Kobayashi and S. Nagayama, J. Org. Chem., 1997, 62, 232 CrossRef CAS; S. Kobayashi and S. Nagayama, J. Am. Chem. Soc., 1997, 119, 10 049 CrossRef CAS.
  7. S. J. Veenstra and P. Schmid, Tetrahedron Lett., 1997, 38, 997 CrossRef CAS.
  8. Y. Masuyama, J. Tosa and Y. Kurusu, Chem. Commun., 1999, 1075 RSC.
  9. T. Akiyama and J. Iwai, Synlett, 1998, 273 CAS.
  10. T. Akiyama, J. Takaya and H. Kagoshima, Synlett, 1999, 1045 CrossRef CAS; T. Akiyama, J. Takaya and H. Kagoshima, Chem. Lett., 1999, 947 CrossRef CAS.
  11. T. Akiyama, J. Takaya and H. Kagoshima, Synlett, 1999, 1426 CrossRef CAS.
  12. Use of commercially available BF3·2AcOH gave comparable results.
  13. Brønsted acid, generated from BF3·OEt2 and 0.5 equiv. of AcOH, may be the active species. For examples of the intramolecular allylation of imines with allylstannanes wherein protic acids have been employed, see: I. Kadota, J.-Y. Park and Y. Yamamoto, Chem. Commun., 1996, 841 Search PubMed; J.-Y. Park, I. Kadota and Y. Yamamoto, J. Org. Chem., 1999, 64, 4901 RSC.
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