Central versus Terminal Attack in Nucleophilic Addition to (π-Allyl)palladium Complexes. Ligand Effects and Mechanism

Abstract

Nucleophilic addition to (η3-2-chloropropenyl)palladium complexes 1 with stabilized carbanions such as dialkyl malonates was studied. These complexes are used as probes to determine whether nucleophilic attack occurs at the central or terminal carbon of the π-allyl group. Attack at the central carbon leads to substitution of chloride via a palladacyclobutane intermediate. The regiochemistry of the reaction (central versus terminal attack) is controlled by proper choice of ligands. Thus, σ-donor ligands direct the attack of the nucleophile to the central carbon (C-2) of the allyl group whereas π-acceptor ligands direct the attack to the terminal carbons (C-1 or C-3). It was found that there is a correlation between the relative rate of central versus terminal attack and the 13C NMR shifts of the allyl group. The shift difference between the central and terminal carbons, Cc − Ct, can be used to predict the site of attack. Ab initio calculations were performed on (π-allyl)palladium complexes as well as on th...