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DOI: 10.1039/A904126E (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 1, 1999, 2057-2060

New reaction conditions using trifluoroethanol for the E-I Hofmann rearrangement

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Yoshihiro Matsumura, Yuki Satoh, Kimihiro Shirai, Osamu Onomura and Toshihide Maki

Abstract

The Hofmann rearrangement of N2-protected glutamine esters to N2-protected (2S[hair space])-4-[(2,2,2-trifluoroethoxy)carbonylamino]-2-aminobutyric acid esters was successfully achieved by an electrochemical method using a trifluoroethanol (TFE)–MeCN solvent system where the TFE may play an important role in controlling the basicity caused by electrochemically generated bases.

References

  1. (a) E. F. Wallis and J. F. Lane, Org. React. (N.Y.), 1946, 3, 267; (b) C. H. Senanayake, L. E. Fredenburgh, R. A. Reamer, R. D. Larsen, T. R. Verhoeven and P. J. Reider, J. Am. Chem. Soc., 1994, 116, 7947 CrossRef CAS and references cited therein.
  2. (a) H. E. Baumgarten, H. L. Smith and A. J. Staklis, J. Org. Chem., 1975, 40, 3554 CrossRef CAS; (b) A. S. Radhakrishna, M. E. Parham, R. M. Riggs and G. M. Loundon, J. Org. Chem., 1979, 44, 1746 CrossRef CAS; (c) G. M. Loundon, A. S. Radhakrishna, M. R. Almond, J. K. Blodgett and R. H. Boutin, J. Org. Chem., 1984, 49, 4272 CrossRef; (d) G. M. Loundon and R. H. Boutin, J. Org. Chem., 1984, 49, 4277 CrossRef; (e) M. Tamura, J. Jacyno and C. H. Stammer, Tetrahedron Lett., 1986, 27, 5435 CrossRef CAS; (f) S.-S. Jew, H. G. Park, H.-J. Park, M.-S. Park and Y.-S. Cho, Tetrahedron Lett., 1990, 31, 1559 CrossRef CAS.
  3. (a) T. Shono, Y. Matsumura, S. Yamane and S. Kashimura, Chem. Lett., 1982, 565 CAS; (b) Y. Matsumura, T. Maki and Y. Satoh, Tetrahedron Lett., 1997, 38, 8879 CrossRef CAS.
  4. M. M. Baizer, in Organic Electrochemistry, ed. H. Lund and M. M. Baizer, Marcel Dekker, New York, 1991, p. 1265 Search PubMed.
  5. (a) S. H.-Kabab, K. Lavrador, J. P. Bazureau and J. Hamelin, Synth. Commun., 1995, 25, 2223; (b) B. Imperiali, K. L. Shannon, M. Unno and K. W. Rickert, J. Am. Chem. Soc., 1992, 114, 7944 CrossRef CAS; (c) G. Filsak, K. Taraz and H. Budzikiewicz, Z. Naturforsch., C: Biosci., 1994, 49, 18 Search PubMed.
  6. E. Sondheimer and R. W. Holley, J. Am. Chem. Soc., 1957, 79, 3767 CrossRef CAS.
  7. T. Shiba, A. Koda, S. Kusumoto and T. Kaneko, Bull. Chem. Soc. Jpn., 1968, 41, 2748 CAS.
  8. T. Poloñski, J. Chem. Soc., Perkin Trans. 1, 1988, 639 RSC.
  9. The mechanism for the selective methanolysis of the carbamoyl group of 6a to give 11 is not clear but a similar solvolysis of (–)-asparagine under basic conditions has been reported: J. S. Amato, C. Bagner, R. J. Cvetovich, S. Gomolka, F. W. Hartner, Jr. and R. Reamer, J. Org. Chem., 1998, 63, 9533 Search PubMed.
  10. J. A. Riddick, W. B. Bunger and T. K. Sakano, in Organic Solvents, 4th edn., John Wiley & Sons, New York, 1986, p. 700 Search PubMed.
  11. TFE has been used as a solvent for electrochemical oxidation: (a) J. Y. Becker, B. E. Smart and T. Fukunaga, J. Org. Chem., 1988, 53, 5714 CrossRef CAS; (b) Y. Matsumura, T. Tomita, M. Sudoh and N. Kise, Tetrahedron Lett., 1994, 35, 1271 CrossRef CAS.
  12. R. Liu and W. C. Still, Tetrahedron Lett., 1993, 34, 2573 CrossRef CAS.
  13. C. A. Wartchow, P. Wang, M. D. Bednarski and M. R. Callstrom, J. Org. Chem., 1995, 60, 2216 CrossRef CAS.
  14. A. A. Mazurov, S. A. Andronati, T. I. Korotenko, V. Y. Gorbatyuk and Y. E. Shapiro, Int. J. Pept. Protein Res., 1993, 42, 14 CAS.
  15. K. Karagiannis, A. Manolopoulou, G. Stavropoulos, C. Poulos, C. C. Jordan and R. M. Hagan, Int. J. Pept. Protein Res., 1991, 38, 350 CAS.
  16. S. Tsubotani, Y. Funabashi, M. Takamoto, S. Hakoda and S. Harada, Tetrahedron, 1991, 47, 8079 CrossRef.
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