Abstract
The supported aqueous phase methodology was applied to the catalytic system Pd(OAc)2/5TPPTS, a catalyst precursor of the Trost–Tsuji reaction. The characterization of the solid by 31P MAS NMR spectroscopy confirms the reduction by the phosphines of Pd(II) to Pd(0) as Pd(TPPTS)3. The catalytic properties of this solid were determined for the allylic substitution of (E)-cinnamyl ethyl carbonate by nucleophiles such as ethyl acetoacetate, dimethyl malonate, morpholine, phenol and 2-mercaptopyridine and were compared to those of the same catalytic system in a biphasic water/nitrile medium. Having demonstrated the absence of palladium leaching and having solved the problem of water leaching from the solid into the organic solvent, the SAP Pd catalyst was engaged with success in a continuous flow experiment, demonstrating the possibility to reach a productivity superior to 2200 moles of carbonate selectively converted per mole of palladium within 11 h.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
J. Tsuji, H. Takahashi and M. Morikawa, Tetrahedron (1965) 4387.
J. Tsuji, Palladium Reagents and Catalysts (Wiley, New York, 1995).
B.M. Trost, Acc. Chem. Res. 29 (1996) 355.
B.M. Trost and D.L. van Vranken, Chem. Rev. 96 (1996) 395.
C. Amatore, E. Bart, J.P. Genêt, A. Jutand, S. Lemaire-Audoire and M. Savignac, J. Org. Chem. 60 (1995) 6829.
G.C. Frost, J. Horwarth and J.J.M. Williams, Tetrahedron: Asymm. 3 (1992) 1089.
B.M. Trost and E. Keinan, J. Am. Chem. Soc. 100 (1978) 7779.
D.E. Bergbreiter and D.A. Weatherford, J. Org. Chem. 54 (1989) 2726.
P.A. Griego, ed., Organic Synthesis in Water (1998) ch. 5, p. 172; and, eds., Aqueous-Phase Organometallic Catalysis (1998) p. 401.
S. dos Santos, Y. Tong, F. Quignard, A. Choplin, D. Sinou and J.P. Dutasta, Organometallics 17 (1998) 78.
E. Blart, J.P. Genêt, M. Safi, M. Savignac and D. Sinou, Tetrahedron 50 (1994) 505
S. Sigismondi and D. Sinou, J. Mol. Catal. 116 (1997) 289.
C. Goux, M. Massacret, P. Lhoste and D. Sinou, Organometallics 14 (1995) 4585.
C. Goux, P. Lhoste and D. Sinou, Tetrahedron 50 (1994) 10321.
J.A. Riddick and W.B. Bunger, in: Organic Solvents, Physical Properties and Methods of Purification, Techniques of Chemistry, Vol. II, 3rd Ed. (Wiley, New York, 1970).
J. March, Advanced Organic Chemistry, 3rd Ed. (Wiley, New York, 1985) p. 220.
J.P. Arhancet, M.E. Davis, J.S. Merola and B.E. Hanson, Nature 339 (1989) 454; M.E. Davis, CHEMTECH 22 (1992) 498.
J.P. Arhancet, M.E. Davis, J.S. Merola and B.E. Hanson, J. Catal. 121 (1990) 327.
G. Fremy, E. Monflier, J.F. Carpentier, Y. Castanet and A. Mortreux, Angew. Chem. Int. Ed. Engl. 34 (1995) 1474.
E. Fache, C. Mercier and N. Pagnier, J. Mol. Catal. 79 (1993) 117.
J.P. Arhancet, M.E. Davis and B.E. Hanson, J. Catal. 129 (1991) 11.
K.T. Wan and M.E. Davis, Nature 370 (1994) 449; K.T. Wan and M.E. Davis, J. Catal. 148 (1994) 1.
L. Tonks, M.M. Anson, K. Hellgardt, A.R. Mirza, D.R. Thompson and J.M.J. Williams, Tetrahedron Lett. 38 (1997) 4319; M.S. Anson, M.P. Leese, L. Tonks and J.M.J. Williams, J. Chem. Soc. Dalton Trans. (1998) 3529.
I.T. Horvath, Catal. Lett. 6 (1990) 43.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
dos Santos, S., Quignard, F., Sinou, D. et al. Allylic substitution catalysed by silica-supported aqueous phase palladium(0) catalysts. Topics in Catalysis 13, 311–318 (2000). https://doi.org/10.1023/A:1009082216524
Issue Date:
DOI: https://doi.org/10.1023/A:1009082216524