Elsevier

Journal of Molecular Catalysis

Volume 32, Issue 2, 1 September 1985, Pages 211-218
Journal of Molecular Catalysis

Metals in organic syntheses: Part XII1. hydrocarboalkoxylation of ethyl 3-butenoate catalyzed by palladium complexes

https://doi.org/10.1016/0304-5102(85)80007-9Get rights and content

Abstract

The effects of the main reaction parameters on yield and regioselectivity in the hydrocarboalkoxylation of ethyl 3-butenoate, catalyzed by a [PdCl2(PPh3)2]-PPh3 system, have been investigated. A higher regioselectivity towards diethyl glutarate is obtained in a polar solvent, such as ethanol, or in the presence of higher concentrations of added PPh3 or under low carbon monoxide pressure. As a general trend, higher regioselectivity is obtained at the expense of the yield.

In ethanol, high yields but low regioselectivities are obtained when the catalyst is employed together with HCl; in benzene the presence of HCl strongly inhibits the catalysis.

In the presence of molecular hydrogen no hydroformylation occurs, the yield is much higher and the regioselectivity remains practically the same; moreover, the inhibitory effect of HCl is suppressed.

The palladium catalyst is highly active and regioselective in the presence of SnCl2.

References (17)

  • J. Tsuji et al.

    Tetrahedron Lett.

    (1963)
  • G. Cavinato et al.

    J. Mol. Catal.

    (1981)
  • G. Cavinato et al.

    J. Organometall. Chem.

    (1982)
  • L.M. Venanzi

    Coord. Chem. (IUPAC)

    (1981)
  • I. Schwager et al.

    J. Catal.

    (1976)
  • R. Bardi et al.

    J. Organometall. Chem.

    (1982)
  • R. Bardi et al.

    J. Organometall. Chem.

    (1982)
  • G. Cavinato et al.

    J. Organometall. Chem.

    (1983)
There are more references available in the full text version of this article.

Cited by (19)

  • Palladium complexes of (benzoimidazol-2-ylmethyl)amine ligands as catalysts for methoxycarbonylation of olefins

    2015, Journal of Molecular Catalysis A: Chemical
    Citation Excerpt :

    In recent years, a number of Pd complexes containing varied ligand architectures have been reported to show high activity as well as selectivity for methoxycarbonylation of olefins such as styrene1, 1-hexene [11] or ethene [12] under mild reaction conditions. For instance, under low partial pressures of carbon monoxide and moderate temperatures, some of these catalyst systems show high regioselectivity (>90%) towards branched esters [13–25]. Currently, one such catalyst design that is attracting significant attention are the mixed nitrogen–phosphine donor Pd complexes.

  • Progress in hydroformylation and carbonylation

    1995, Journal of Molecular Catalysis. A, Chemical
View all citing articles on Scopus
1

Part XI:see [1].

2

Author to whom correspondence should be addressed.

View full text