Total synthesis of (±)-Halomon by a Johnson - Claisen rearrangement

Angewandte Chemie - International Edition

Volumn 37, Issue 15, 1998, Pages 2085-2087

  Schlama, Thierry ^a   Baati, Rachid ^a   Gouverneur, Véronique ^a   Valleix, Alain ^b   Falck, John R ^c   Mioskowski, Charles ^a  

^a UNIVERSITÉ DE STRASBOURG   (France)

^b CEA SACLAY   (France)

^c UNIVERSITY OF TEXAS AT DALLAS   (United States)

Author keywords

Antitumour agents; Halomon; Natural products; Rearrangements; Total synthesis

Indexed keywords

EID: 0032541290     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19980817)37:15<2085::AID-ANIE2085>3.0.CO;2-J     Document Type: Article

References (29)

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16. The yield could not go beyond 55% since the product slowly underwent elimination under the rearrangement conditions.
17. The use of three equivalents allowed selective reduction of the ester group with no side reactions resulting from the reduction of the halogen atoms.
18. A. P. Kosikowski, J. Lee, J. Org. Chem. 1990, 55, 863.
19. - instead of ten equivalents gave the cyclized 3-chloro-3-chlorovinyl tetrahydrofuran as the only product in 98% yield.
20. Attempts to convert the silyloxy group directly into a bromide were unsuccessful.
21. The use of guanidinium salts as additives was inspired by the work of Chastrette et al., who described that ammonium salts could be used as efficient additives for the addition of an organomagnesium halide to a carbonyl group: M. Chastrette, R. Amouroux, Bull. Soc. Chim. Fr. 1970, 4348. In our case, the use of an ammonium salt was less efficient than hexaethylguanidinium chloride.
22. J. Cousseau, Synthesis 1980, 805.
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24. H. G. Viehe, Z. Janousek, Angew. Chem. 1973, 85, 837; Angew. Chem. Int. Ed. Engl. 1973, 12, 806; H. G. Viehe, Z. Janousek in Encyclopedia of Reagents for Organic Synthesis, Vol. 3 (Ed.: L. A. Paquette), Wiley, Chichester, 1995, pp. 17019-17210.
25. H. G. Viehe, Z. Janousek, Angew. Chem. 1973, 85, 837; Angew. Chem. Int. Ed. Engl. 1973, 12, 806; H. G. Viehe, Z. Janousek in Encyclopedia of Reagents for Organic Synthesis, Vol. 3 (Ed.: L. A. Paquette), Wiley, Chichester, 1995, pp. 17019-17210.
26. 13C NMR, IR, and MS) and Chromatographic analysis (TLC and HPLC).
27. T. Schlama, R. Baati, V. Gouverneur, C. Mioskowski, unpublished results.
28. During the course of this study, the use of a [2,3]-sigmatropic rearrangement of a carbene as the key step for the synthesis of a polyhalogenated diene of the halomon class was published by M. E. Jung, M. H. Parker, J. Org. Chem. 1997, 62, 7094.
29. New asymmetric [3,3]-sigmatropic rearrangements are under current investigation in our laboratory.