View PDF Version
 
DOI: 10.1039/A806337K (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 1, 1998, 3747-3758

Syntheses of optically active α-amino nitriles by asymmetric transformation of the second kind using a principle of O. Dimroth

(Note: The full text of this document is currently only available in the PDF Version )

Nasser A. Hassan, Erwin Bayer and Johannes C. Jochims

Abstract

A mixture of solids As and Bs in equilibrium with the dissolved compounds A1 and B1 is transformed completely into one pure solid, say Bs, if the dissolved compounds A1⇌B1 are equilibrating in solution. This is applied to transform 1∶1 mixtures of solid diastereomeric amygdalates (2-hydroxy-2-phenylacetates; mandelates) (R,R)-3 + (S,R)-3 prepared from racemic α-amino nitriles (R,S[hair space])-1 with (R)-mandelic acid 2 into stereochemically pure single diastereomers (R,R)-3, or (S,R)-3 (de > 97%) (‘asymmetric transformation of the second kind by application of Dimroth’s principle’). Decomposition of the amygdalates (R,R)-3, or (S,R)-3, with aqueous base affords the enantiomerically pure α-amino nitriles (R)-1, or (S[hair space])-1 (ten examples). The chiral auxiliary (R)-mandelic acid is recovered almost quantitatively. The optically active α-amino nitriles are hydrolyzed to amides 6, and further to α-N-alkylamino acids 7. N-Benzylamino acids 7 are hydrogenated to α-amino acids 8. Some of the optically active α-amino nitriles 1 are reduced to optically active 1,2-diamines 9. In most cases, absolute configurations could be assigned by comparison of the specific rotations observed with those of authentic compounds.

References

  1. R. Kuhn, Ber. Dtsch. Chem. Ges., 1932, 65, 49.
  2. E. L. Eliel, S. H. Wilen and L. N. Mander, Stereochemistry Organic Compounds, Wiley, New York, 1994, pp. 364, 1193 Search PubMed.
  3. E. E. Turner and M. M. Harris, Quart. Rev., 1947, 1, 299 Search PubMed.
  4. J. Jaques, A. Collet and S. H. Wilen, Enantiomers, Racemates and Resolutions, Wiley, New York, 1981, p. 370 Search PubMed.
  5. The misleading terms ‘Wrst order’ and ‘second order asymmetric transformation’ resulting from inappropriate translations of Kuhn's definitions should be abandoned (see ref. 2).
  6. R. Kuhn and J. C. Jochims, Justus Liebigs Ann. Chem., 1961, 641, 143 CAS.
  7. O. Dimroth, Justus Liebigs Ann. Chem., 1910, 377, 127.
  8. K. Weinges, K.-P. Klotz and H. Droste, Chem. Ber., 1980, 113, 710 CAS.
  9. T. Shiraiwa, K. Shinjo and H. Kurokawa, Bull. Chem. Soc. Jpn., 1991, 64, 3251 CAS.
  10. J. D. Moseley, B. J. Williams, S. N. Owen and H. M. Verrier, Tetrahedron: Asymmetry, 1996, 7, 3351 CrossRef CAS.
  11. R. Yoshioka, O. Ohtsuki, M. Senuma and T. Tosa, Chem. Pharm. Bull., 1989, 37, 883 CAS and references therein.
  12. R. Grigg, Chem. Soc. Rev., 1987, 16, 89 RSC.
  13. P. J. Reider, P. Davis, D. L. Hughes and E. J. J. Grabowski, J. Org. Chem., 1987, 52, 955 CrossRef CAS.
  14. T. Shiraiwa, Y. Baba, H. Miyazaki, S. Sakata, S. Kawamura, M. Uehara and H. Kurokawa, Bull. Chem. Soc. Jpn., 1993, 66, 1430 CAS and references therein.
  15. J. C. Clark, G. H. Philipps, M. R. Steer and L. Stephenson, J. Chem. Soc., Perkin Trans. 1, 1976, 471 RSC.
  16. J. C. Clark, G. H. Philipps and M. R. Steer, J. Chem. Soc., Perkin Trans. 1, 1976, 475 RSC.
  17. W. H. Boesten, Eur. Pat. Appl. 0442584 A1 (Chem. Abstr., 1992, 116, 42062r) Search PubMed.
  18. W. H. Boesten, Eur. Pat. Appl. 0442584 A1 (Chem. Abstr., 1992, 116, 42063s) Search PubMed.
  19. V. I. Tararov, T. F. Savel'eva, N. Yu. Kuznetsov, N. S. Ikonnikov, S. A. Orlova, Yu. N. Belokon and M. North, Tetrahedron: Asymmetry, 1997, 8, 79 CrossRef CAS.
  20. V. S. Parmar, A. Singh, K. S. Bisht, N. Kumar, Y. N. Belokon, K. A. Kochetkov, N. S. Ikonnikov, S. A. Orlova, V. I. Tararov and T. F. Saveleva, J. Org. Chem., 1996, 61, 1223 CrossRef CAS.
  21. W. J. Boyle, S. Sifniades and J. F. Van Peppen, J. Org. Chem., 1979, 44, 4841 CrossRef CAS and references therein.
  22. C. Hongo, M. Tohyama, R. Yoshioka, S. Yamada and I. Chibata, Bull. Chem. Soc. Jpn., 1985, 58, 433 CAS and references therein.
  23. H. Kubota, A. Kubo, M. Takahashi, R. Shimizu, T. Da-te, K. Okamura and K. Nunami, J. Org. Chem., 1995, 60, 6776 CrossRef CAS and references therein.
  24. H. Kunz, in Houben-Weyl, ed. G. Helmchen, R. W. Hoffmann, J. Mulzer and E. Schaumann, Thieme, Stuttgart, 1995, 4th edn., vol. E21, pp. 1931 ff Search PubMed.
  25. K. Weinges, H. Brachmann, P. Stahnecker, H. Rodewald, M. Nixdorf and H. Irngartinger, Justus Liebigs Ann. Chem., 1985, 566 Search PubMed.
  26. K. Weinges and H. Blackholm, Chem. Ber., 1980, 113, 3098 CAS and references therein.
  27. H. Kunz, W. Sager, D. Schanzenbach and M. Decker, Justus Liebigs Ann. Chem., 1991, 649 Search PubMed.
  28. G. J. Matthews, Fr. Pat. Appl., 2,141,354 (Chem. Abstr., 1973, 79, 42210e) Search PubMed.
  29. T. A. Hylton and F. L. Shenton, U.S. Pat. Appl., 4,072,698 (Chem. Abstr., 1978, 88, 152276z) Search PubMed.
  30. I. Ojima, S. Inaba, K. Nakatsugawa and Y. Nagai, Chem. Lett., 1975, 331 CAS.
  31. I. Ojima, S. Inaba and Y. Nagai, Chem. Lett., 1975, 737 CAS.
  32. W. J. Greenlee, J. Org. Chem., 1984, 49, 2632 CrossRef CAS.
  33. F. Texier-Boullet, Synthesis, 1985, 679 CAS.
  34. K. Mai and G. Patil, Org. Prep. Proced. Int., 1985, 17, 183 CAS.
  35. T. Hanafusa, J. Ichihara and T. Ashida, Chem. Lett., 1987, 687 CAS.
  36. M. P. Georgiadis and S. A. Haroutounian, Synthesis, 1989, 616 CrossRef CAS.
  37. C. Cativiela, M. D. Díaz-de-Villegas, J. A. Gálvez and J. I. García, Tetrahedron, 1996, 52, 9563 CrossRef CAS.
  38. W. E. McEwen, A. V. Grossi, R. J. MacDonald and A. P. Stamegna, J. Org. Chem., 1980, 45, 1301 CrossRef CAS.
  39. W. L. Matier, D. A. Owens, W. T. Comer, D. Deitchman, H. C. Ferguson, R. J. Seidehamel and J. R. Young, J. Med. Chem., 1973, 16, 901 CrossRef CAS.
  40. A. A. Shaikh, Vidya B, 1976, 19, 137 (Chem. Abstr., 1978, 88, 136524y) Search PubMed.
  41. N. Moss, J. Ferland, S. Goulet, I. Guse, E. Malenfant, L. Plamondon, R. Plante and R. Déziel, Synthesis, 1997, 32 CrossRef CAS.
  42. M. Mori, H. Imma and T. Nakai, Tetrahedron Lett., 1997, 38, 6229 CrossRef CAS.
  43. M. Miyoshi, Bull. Chem. Soc. Jpn., 1973, 46, 212 CAS.
  44. I. T. Barnish, P. E. Cross, J. C. Danilewicz, R. P. Dickinson and D. A. Stopher, J. Med. Chem., 1981, 24, 399 CrossRef CAS.
  45. T. Inaba, I. Kozono, M. Fujita and K. Ogura, Bull. Chem. Soc. Jpn., 1992, 65, 2359 CAS.
  46. Y. Ohfune, N. Kurokawa, N. Higuchi, M. Saito, M. Hashimoto and T. Tanaka, Chem. Lett., 1984, 441 CAS.
  47. D. W. Russell, J. Chem. Soc., 1962, 753 RSC.
  48. P. Quitt, J. Hellerbach and K. Vogler, Helv. Chim. Acta, 1963, 46, 327 CAS.
  49. W. A. H. Huffman and A. W. Ingersoll, J. Am. Chem. Soc., 1951, 73, 3366 CrossRef CAS.
  50. K. Eisler, J. Rudinger and F. Sorm, Collect. Czech. Chem. Commun., 1966, 31, 4563 CAS.
  51. L. R. Overby and A. W. Ingersoll, J. Am. Chem. Soc., 1951, 73, 3363 CrossRef CAS.
  52. K. Masuda, J. Adachi and K. Nomura, J. Chem. Soc., Perkin Trans. 1, 1981, 1033 RSC.
  53. D. N. Harcourt and R. D. Waigh, J. Chem. Soc. (C), 1971, 967 RSC.
  54. E. M. Gal, J. Am. Chem. Soc., 1949, 71, 2253 CrossRef CAS.
  55. K. Weinges, G. Brune and H. Droste, Justus Liebigs Ann. Chem., 1980, 212 Search PubMed.
  56. D. C. Horwell, M. C. Pritchard, R. S. Richardson, E. Roberts and J. Aranda, Eur. Pat. Appl. EP 405,537 (Chem. Abstr., 1991, 115, 50307u) Search PubMed.
  57. D. Matosiuk, J. Stefanczyk and T. Tkaczynski, Pharmazie, 1997, 52, 71 Search PubMed.
  58. A. Funke and P. Kornmann, Bull. Soc. Chim. Fr., 1949, 241 CAS.
  59. S. Berger and A. Nudelman, Arch. Pharm., 1990, 323, 229 CAS.
Click here to see how this site uses Cookies. View our privacy policy here.