Convenient cleavage of water-insoluble allylic substrates in the presence of per(2,6-di-O-methyl)-β-cyclodextrin

Synlett

Volumn , Issue 5, 2000, Pages 722-724

  Widehem, Rodrigue ^a   Lacroix, Thibaut ^a   Bricout, Herve ^a   Monflier, Eric ^a  

^a UNIVERSITÉ D'ARTOIS   (France)

Author keywords

Allylic compounds; Cleavage; Cyclodextrin; Palladium; Phase transfer catalysis

Indexed keywords

CYCLODEXTRIN; PALLADIUM;

ARTICLE; CATALYSIS; ENZYME SUBSTRATE COMPLEX; FRANCE; SOLUBILITY; SYNTHESIS;

EID: 0034077815     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: None     Document Type: Article

References (30)

1. Goldberg, Y. Phase Transfer Catalysis, Selected Problems and Applications; Gorden and Breach Science Publishers: Amsterdam, 1992.
2. (a) Okano, T. In Aqueous-Phase Organometallic Catalysis, Cornils, B.; Herrmann, W.A., Eds.; Wiley-VCH, Weinheim, Germany 1998, p. 221.
3. (b) Monflier, E. Recent Res. Devel. In Organic Chem. 1998, 2, 623.
4. (c) Monflier, E.; Blouet, E.; Barbaux, Y.; Mortreux, A. Angew. Chem. Int. Ed. Engl. 1994, 33, 2100.
5. (d) Monflier, E.; Tilloy, S.; Castanet, Y.; Bertoux, R; Mortreux, A. New J. Chem. 1997, 27, 857.
6. (e) Monflier, E.; Fremy, G.; Castanet, Y.; Mortreux, A. Angew. Chem. Int. Ed. Engl. 1995, 34, 2269.
7. Lacroix, T.; Bricout, H.; Tilloy, S.; Monflier E. Eur. J. Org. Chem. 1999, 3127.
8. The per(2,6-di-O-methyl)-β-cyclodextrin was supplied by Aldrich Chemical Co and was used without further purification. This cyclodextrin is a mixture of randomly methylated β-cyclodextrins. In particular, electrospray mass spectrum exhibits signals at m/z 1311, 1325, 1339, 1353, 1367 and 1381 corresponding to the different degrees of methylation. The average number of substituted hydroxyl group was equal to 14.
9. (a) Jeffrey, P.D.; Mc Combie, S.W. J. Org. Chem. 1982, 47, 587.
10. (b) Kunz, H.; Waldmann, H.; Klinkhammer, U. Helv. Chim. Acta. 1988, 71, 1868.
11. (c) Merzouk, A.; Guibe, F.; Loffet, A. Tetrahedron Lett. 1992, 33, 477.
12. (d) Minami, I.; Ohashi, Y.; Shimizu, I.; Tsuji. J. Tetrahedron Lett. 1985, 26, 2449.
13. (e) Kunz, H.; Unverzagt. C. Angew. Chem. Int. Ed. Engl. 1984, 23, 436.
14. (f) Hayakawa, Y.; Wakabayashi, S.; Kato, H.; Noyori, R. J. Am. Chem. Soc. 1990, 112, 1691.
15. (g) Garon-Helion, F.; Merzouk, A.; Guibe, F. J. Org. Chem. 1993, 58, 6109.
16. (h) Guibe, F.; Saint'Leux, Y. Tetrahedron Lett. 1981, 22, 3591.
17. (i) Dangles, O.; Guibé, F.; Balavoine, G.; Lavielle, S.; Marquet, A. J. Org. Chem. 1987, 52, 4984.
18. (a) Genet, J.P.; Blart, E.; Savignac, M.; Lemeune, S.; Paris, J.M. Tetrahedron Lett. 1993, 34, 4189.
19. (b) Lemaire-Audoire, S.; Savignac, M.; Blart. E.; Pourcelet, G.; Genêt, J.P.; Bernard, J.M. Tetrahedron Lett. 1994, 35, 8783.
20. (c) Genet, J.P.; Blart, E.; Savignac, M.; Lemeune, S.; Lemaire-Audoire, S.; Paris, J.M.; Bernard, J.M. Tetrahedron 1994, 50, 497.
21. (d) Lemaire-Audoire, S.; Savignac, M.; Pourcelet, G.; Genet, J.P.; Bernard, J.M. J. Mol. Catal. 1997, 116, 247.
22. 31P solution NMR indicated that the product was a mixture of TPPTS (ca 98%) and its oxide (ca 2%).
23. 2 for one hour. A shorter stirring period led to non-reproducible results. Formation of catalytic species in the presence of DMCyD is probably not completed before one hour.
24. 13C NMR. The elemental analyses are in good agreement with the proposed structure.
25. 13C NMR. The elemental analyses are in good agreement with the proposed structure.
26. 13C NMR. The elemental analyses are in good agreement with the proposed structure.
27. The initial catalytic activities were calculated as the amount of converted substrate per hour per mole of palladium at 10-20% conversion. The error on the ratio of initial activities was about 10%.
28. No activity was observed in the absence of palladium and /or TPPTS, proving undoubtedly that the methylated cyclodextrin cannot catalyze the cleavage of allylic substrates.
29. Fenyvesi, E.; Szente, L.; Russell, N.R.; McNamara, M. In Comprehensive Supramolecular Chemistry, Vol. 3; Atwood, J.L.; Davies, J.E.D.; MacNicol, D.D.; Vögtle, F., Eds.; Pergamon, Oxford 1996, p 305.
30. Sigismondi, S.; Sinou, D. J. Mol. Catal. 1997, 116, 289.