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Journal of the Mexican Chemical Society

versão impressa ISSN 1870-249X

J. Mex. Chem. Soc vol.49 no.2 Ciudad de México  2005

 

Article

 

An Alternative Approach to Aminodiols from Baylis-Hillman Adducts. Stereoselective Synthesis of Chloramphenicol, Fluoramphenicol and Thiamphenicol

 

Cristiano R. Mateus and Fernando Coelho*

 

Instituto de Química, Universidade Estadual de Campinas, CP 6154, 13083-970 Campinas - SP, Brazil. * e-mail: coelho@iqm.unicamp.br

 

Received: September 21, 2004
Published on the web: March 15, 2005

 

Abstract

We describe herein a new approach for the stereoselective synthesis of broad spectrum antibiotics from Baylis-Hillman adducts. The strategy is based on the preparation of an ene-carbamate directly from a Baylis-Hillman adduct using a Curtius rearrangement reaction. Stereoselective hydroboration furnished a mixture of diastereoisomeric aminoalcohols (syn and anti). After chromatographic separation, the syn diastereoisomer was directly transformed into the antibiotics.

Keywords: chloramphenicol, Baylis-Hillman, fluoramphenicol, thiamphenicol, α-hydroxy-methylketones

 

Resumo

Descrevemos aqui uma nova interpretação para a espectros de banda larga da síntese estereos-seletiva de antibióticos de adutos Baylis-Hillman. А estrategia é baseada na preparação de um eno-carbamato diretamente do aduto Baylis-Hillman, usando um rearranjo de Curtius. А hidroboração estereosseletiva fornece uma mistura de aminoalcools diasteroisomeros (syn e anti). Após separação cromatográfica, o diasteroisomero syn foi diretamente transformado no antibiótico.

 

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Acknowledgments

The authors thank Fapesp for a fellowship to CRM (01/01558-8) and for financial support (02/00461-3) and CNPq (301369/1989-9) for a research fellowship to FC. The authors are grateful to Prof. C. H. Collins for English corrections of this manuscript.

 

References

1. Aguilar, L.; Gimenez, M. J.; Garcia-Rey, C.; Martin, J. E.; J. Antimicrob. Chemother. 2002, 50, 93.         [ Links ]

2. Lautenbach, E.; Gould, C. V.; La Rosa, L. A.; Marr, A. M.; Fishman, N. O.; Becker, W. B.; Nachamkin, I.; Int. J. Antimicrob. Agents 2004, 23, 200;         [ Links ] Boulos, A.; Rolain, J. M.; Raoult, D.; Antimicrob. Agents. Chemother. 2004, 48, 747;         [ Links ] Zhanel, G. G.; Laing, N. M.; Nichol, K. A.; Palatvek, L. P.; Noreddin, A.; Hisanaga, T.; Johnson, J. L.; Hoban, D. J.; J. Antimicrob. Chemother. 2003, 52, 382;         [ Links ] Cunrie, B. J.; Eur. Respi. J. 2003, 22, 542.         [ Links ]

3. Xaplanteri, M. A.; Andreou, A.; Dinos, G. P.; Kalpaxis, D. L.; Nucleic Acids Res. 2003, 32, 5074;         [ Links ] Isenberg, S. J.; J. AAPOS 2003, 7, 307.         [ Links ]

4. Ungheri, D.; Licciardello, L.; PCT Int. Appl. WO 060344, 2001 (CA 135:162487);         [ Links ] Colombo, G.; Ungheri, D.; Licciardello, L.; Giromondo, M.; Drago, L. PCT Int. Appl. WO 076585, 2001 (CA 135: 198756).         [ Links ]

5. Ehrlich, J.; Bartz, Q. R.; Smith, R. M.; Joslyn, D. A.; Burkholder, P. R.; Science 1947, 106, 417;         [ Links ] Bartz, Q.R.; J. Biol. Chem. 1948, 172, 445;         [ Links ] Smith, R. M.; Joslyn, D. A.; Gruhzit, O. M.; McLean, W. I.; Penner, M. A.; Ehrlich, J.; J. Bacteriol. 1948, 55, 425;         [ Links ] Bartz, Q.R.; J. Clin. Invest. 1949, 28, 1051.         [ Links ]

6. For examples of classical industrial synthesis of chloramphenicol and related antibiotics, see: Ehrlich, J.; Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley & Sons: New York, 1978, vol. 2., p. 920.         [ Links ]

7. For some syntheses of racemic chloramphenicol, see: Controulis, J.; Rebstock, M. C.; Crooks, Jr., H. M.; J. Am. Chem. Soc. 1949, 71, 2463;         [ Links ] Long, L. M.; Troutman, H. D.; J. Am. Chem. Soc. 1949, 71, 2469 and 2473;         [ Links ] Ehrhart, G.; Siedel, W.; Nahm, H.; Chem. Ber. 1957, 90, 2088;         [ Links ] Horak, V.; Moezik, F. ; Klein, R. F. X.; Giordano, C.; Synthesis 1984, 839;         [ Links ] Hazra, B. G.; Pore, V. S.; Maybhate, S. P.; Synth. Commun. 1997, 27, 1857.         [ Links ]

8. For some chiral syntheses of chloramphenicol and fluoramphenicol, see: Chenevert, R.; Thiboutot, S.; Synthesis 1989, 444;         [ Links ] Schollkopf, U.;Beulshausen, T.; LiebigsAnn. Chem. 1989, 223;         [ Links ] Rao, A. V. R.; Rao, S. P.; Bhanu, M. N.; J. Chem. Soc., Chem.Commun. 1992, 859;         [ Links ] Lou, B.-L.; Zhang, Y.-Z.; Dai, L.-X.; Chem. Ind. 1993, 7, 249;         [ Links ] Easton, C. J.; Hutton, C. A. ; Merrett, M. C.; Tiekink, E. R. T.; Tetrahedron 1996, 52, 7025;         [ Links ] Veeresa, G.; Datta, A.; Tetrahedron Lett. 1998, 39, 8503;         [ Links ] Corey, E. J.; Choi, S.; Tetrahedron Lett. 2000, 41, 2765;         [ Links ] Park, J. N.; Ko, S. Y.; Koh, H. Y.; Tetrahedron Lett. 2000, 41, 5553;         [ Links ] Loncaric, C.; Wulff, W. D.; Org. Lett. 2001, 3, 3675;         [ Links ] Baskhar, G. ; Kumar, V.S.; Rao, B.V.; Tetrahedron:Asymmetry 2004, 15, 1279.         [ Links ]

9. For some racemic syntheses of thiamphenicol, see: McCombie, S. W.; Nagabhushan, T. L.; Tetrahedron Lett. 1987, 28, 5395;         [ Links ] Giordano, C.; Cavicchioli, S.;Levi, S.; Villa, M.; Tetrahedron Lett. 1988, 29, 5561.         [ Links ]

10. For some asymmetric syntheses of thiamphenicol and florfenicol, see: Giordano, C.; Cavicchioli, S.; Levi, S.; Villa, M.; J. Org. Chem. 1991, 56, 6114;         [ Links ] Davis, F. A.; Zhou, P.; Tetrahedron Lett. 1994, 35, 7525;         [ Links ] Wu, G.-Z.; Tormos, W. I.; PTC Int. Appl.WO 94/14764, 1994 (CA 121: 133722);         [ Links ] Gennari, C.; Pain, G.; Tetrahedron Lett. 1996, 37, 3747;         [ Links ] Wu, G.-Z.; Schumacher, D. P.; Tormos, W.; Clark, J. E.; Murphy, B. L.; J. Org. Chem. 1997, 62, 2996;         [ Links ] Gennari, C.; Vulpetti, A.; Pain, G.; Tetrahedron 1997, 53, 5909;         [ Links ] Kaptein, B.;Dooren, T. J. G. M. V.; Boesten, W. H. J.; Sonke, T.; Duchateau, A. L. L.; Broxterman, Q. B.; Kamphuis, J.; Org. Process Res. Dev. 1998, 2, 10;         [ Links ] Nagabhushan, T.L.; U. S. Patent 4 235 892, 1980 (CA 94: 139433).         [ Links ]

11. Rossi, R.C.; Coelho, F.; Tetrahedron Lett. 2002, 43, 2797.         [ Links ]

12. Coelho, F.; Veronese, D.; Lopes, E.C.S.; Rossi, R.C.; Tetrahedron Lett. 2003, 44, 5731.         [ Links ]

13. For comprehensive reviews on the Baylis-Hillman reaction see: Basavaiah, D.; Rao, A. J.; Satyanarayama, T.; Chem. Rev. 2003, 103, 811;         [ Links ] Almeida, W. P.; Coelho, F.; Quim. Nova 2000, 23, 98 (CA 132: 236562e);         [ Links ] Ciganek, E.; Org. React. 1997, 51, 201;         [ Links ] Basavaiah, D.; Rao, P. D.;. Hyma, R. S.; Tetrahedron 1996, 52, 8001.         [ Links ] For some new insights about the mechanism of the Baylis-Hillman reaction see: Santos, L.S.; Pavam, C.H. Almeida, W.P.; Coelho, F.; Eberlin, M.N.; Angew. Chem. Int. Ed. 2004, 43, 4330.         [ Links ]

14. For some examples of the application of Baylis-Hillman adducts as starting material for the synthesis of natural products see: Almeida, W. P.; Coelho, F.; Tetrahedron Lett. 2003, 44, 937;         [ Links ] Feltrin, M. A.; Almeida, W. P.; Synth. Commun. 2003, 33, 1141;         [ Links ] Mateus, C. R.; Feltrin, M. P.; Costa, A. M.; Coelho, F.; Almeida, W. P.; Tetrahedron 2001, 57, 6901;         [ Links ] Iwabuchi, Y.; Furukawa, M.; Esumi, T.; Hatakeyama, S.; Chem. Commun. 2001, 2030;         [ Links ] Iwabuchi, Y.; Sugihara, T.; Esumi, T.; Hatakeyama, S.; Tetrahedron Lett. 2001, 42, 7867;         [ Links ] Masunari, A.; Trazzi, G.; Ishida, E.; Coelho, F.; Almeida, W. P.; Synth. Commun. 2001, 31, 2100;         [ Links ] Ameer, F.; Drewes, S. E.; Houston-McMillan, M. S.; Kaye, P.T.; S. Afr. J. Chem. 1986, 39, 57;         [ Links ] Hofmann, H. M. R.; Rabe, J.; Helv. Chim. Acta 1984, 67, 413;         [ Links ] Hofmann, H. M. R.; Rabe, J.; J. Org. Chem. 1985, 50, 3849;         [ Links ] Drewes, S. E.; Emslie, N. D.; J. Chem. Soc. Perkin Trans. 1 1982, 2079.         [ Links ]

15. Bergmeier, S.C.; Tetrahedron 2000, 56, 2561 and references cited therein;         [ Links ] Gonzalez-Resende, M.E.; Jorda-Gregori, M.E.; Sepulveda-Arques, J.; Orena, M.; Tetrahedron:Asymmetry 2004, 15, 419 and references cited therein;         [ Links ] Beardsley, D. A.; Fisher, G. B.; Goralski, C. T.; Nicholson, L. W.; Singaram, B.; Tetrahedron Lett. 1994, 35, 1511;         [ Links ] Moody, M. H.; Kaptein, B.; Broxterman, Q. B.; Boesten, W. H. J.; Kamphuis, J.; Tetrahedron Lett. 1994, 35, 1777;         [ Links ] Sasai, H.; Kim, W.; Suzuki, T.; Shibasaki, M.; Tetrahedron Lett. 1994, 35, 6123.         [ Links ]

16. Almeida, W. P.; Coelho, F. Tetrahedron Lett. 1998, 39, 8609;         [ Links ] Coelho, F.; Almeida, W. P.; Mateus, C. R.; Veronese, D.; Lopes, E. C. S.; Silveira, G. P. C.; Rossi, R. C.; Pavam, C. H.; Tetrahedron 2002, 58, 7437.         [ Links ]

17. Braibante, M.E.F.; Braibante, H.S.; Costenaro, J.H.; Synthesis 1999, 943;         [ Links ] van Well, R.M.; Overkleeft, H.S.; van Boom, J.H.; Coop, J.H.; Wang, J.B.; Wang, N.Y.; van der Marel, G.A.; Overhand, M.; Eur. J. Org. Chem. 2003, 9, 1704;         [ Links ] Kedrowski, B.L.; J. Org. Chem. 2003, 68, 5403;         [ Links ] Lu, Y.H.; Taylor, R.T.; Heterocycles 2004, 62, 869;         [ Links ] O'Connor, P.D.; Mander, L.N.; McLachlan, N.W.; Org. Lett. 2004, 6, 703.         [ Links ]

18. Jackson, R.F.W.; Standen, S.P.; Clegg, W.; McCamley, A.; Tetrahedron Lett. 1992, 33, 6197 and references cited therein;         [ Links ] Hoffmann, R.W.; Chem. Rev. 1989, 89, 1841;         [ Links ] Kahn, S.D.; Pau, C.F.; Chamberlin, A.R.; Hehre, W. J.; J. Am. Chem. Soc. 1987, 109, 650 and references cited therein;         [ Links ] Coelho, F.; Almeida, W. P.; Mateus, C. R.; Furtado, L. D.; Gouveia, J. C. F. ; ARKIVOC 2003, X, 443;         [ Links ] Mateus, C.R.; Almeida, W. P.; Coelho, F.; Tetrahedron Lett. 2000, 41, 2533.         [ Links ]

19. Cutler, R.A.; Stenger, R.J.; Suter, C.M.; J. Am. Chem. Soc. 1952, 74, 5475.         [ Links ]

20. For some examples of carbamates prepared from Baylis-Hillman adducts, see: Ciclosi, M.; Fava, C.; Galeazzi, R.; Orena, M.; Sepulveda-Arques, J.; Tetrahedron Lett. 2002, 43, 2199;         [ Links ] Mamaghami, M.; Badrian, A.; Tetrahedron Lett. 2004, 45, 1547;         [ Links ] Xu, L. W.; Xia, C. G.; Tetrahedron Lett. 2004, 45, 4507.         [ Links ]

21. For some industrial strategies for the resolution of racemic mixtures of chloramphenicol and for the inversion of of (2S, 3S) enantiomer, see: Coppi, L.; Giordano, C.; Langoni, A.; Panossian, S. In Chirality in Chemistry II; Collins, A. N.; Sheldrake, G. N; Crosby, J., eds., Wiley: Chichester, 1997, p. 353-362;         [ Links ] Dick, H.; Gradel, W. -D.; Weber, M.; D.E. Patent 3543021, 1987 (CA 107: 197794).         [ Links ]

22. Iwabuchi, Y.; Nakatami, M.; Yokoyama, N.; Hatakeyama, S.; J. Am. Chem. Soc. 1999, 121, 10219.         [ Links ]

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