Umpolung of the allylpalladium reactivity: mechanism and regioselectivity of the electrophilic attack on bis-allylpalladium complexes formed in palladium-catalyzed transformations

The structure and reactivity of various bis-allylpalladium complexes occurring as catalytic intermediates in important synthetic transformations have been studied by applying density functional theory at the B3PW91(DZ + P) level. It was found that n1,n3 coordinated bis-allylpalladium complexes are readily formed from the corresponding n3,n3 complexes, especially in the presence of pi-acceptor phosphine ligands. The theoretical calculations indicate dsigma-->pi type hyperconjugative interactions occurring in the n1-coordinated allyl moiety of the n3,n3 coordinated complexes. These hyperconjugative interactions influence the structure of the complexes and dramatically increase the reactivity of the double bond in the n1-moiety. The DFT results indicate a remarkably low activation barrier for the electrophilic attack on the n1-allyl functionality. In bridged n1,n3 complexes, the electrophilic attack occurs with a very high regioselectivity, which can be explained on the basis of d-pi type hyperconjugative interactions.