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Theses

ETUDE DU MECANISME DE LA REACTION DE TSUJI-TROST
CATALYSEE PAR LES COMPLEXES DU PALLADIUM

Abstract : The 1,3-diphenyl-3-acetoxypropene PhCH=CHPh-OAc is used in the Tsuji-Trost reaction to test chiral ligands efficiency.
We studied its oxidative addition with palladium(0) complex [Pd°(P,P)], generated from Pd(dba)2 + (P,P) (PPh3 or dppb ) or from Pd(PPh3)4. It gives a cationic (eta3-allyl)palladium(II) complex with AcO- as the counter anion. This reaction proceeds through two successive equilibria via a neutral intermediate complex [(eta2-PhCH=CHPh-OAc)Pd°(P,P)].
The nucleophilic substitution on the cationic (eta3-allyl)palladium(II) complex has been studied as well with morpholine and piperidine. With PPh3 this step is irreversible and faster than the oxidative addition, whereas it is reversible with dppb.

The isomerization of cyclic allyl carboxylates such as the cis-5-phenylcyclohex-2-enyl p-Z-benzoates (cis-1Z, Z = NO2, Cl, H, Me, MeO) occurs in the presence of Pd° complexes. Indeed the benzoate ion acts as a nucleophile and reacts with the cationic eta3-allyl complex.
The rate of isomerization of cis-1Z to trans-1Z depends on the catalytic precursor: Pd0(PPh3)4 > {Pd0(dba)2 + 2 PPh3} in agreement with a SN2 mechanism in the isomerization of the cationic (eta3-allyl)palladium complexes formed in the oxidative addition.
We studied the effect of the leaving group on the isomerization at the allylic position. The better the leaving group of the (eta3-allyl)palladium complex, the faster the isomerization is.
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https://tel.archives-ouvertes.fr/tel-00011272
Contributor : Laure Mensah <>
Submitted on : Saturday, December 31, 2005 - 1:21:26 PM
Last modification on : Monday, December 14, 2020 - 9:41:18 AM
Long-term archiving on: : Tuesday, June 15, 2010 - 4:24:31 PM

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  • HAL Id : tel-00011272, version 1

Citation

Laure Mensah. ETUDE DU MECANISME DE LA REACTION DE TSUJI-TROST
CATALYSEE PAR LES COMPLEXES DU PALLADIUM. Catalyse. Université Pierre et Marie Curie - Paris VI, 2005. Français. ⟨tel-00011272⟩

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