Chemodivergent Palladium-Catalyzed Processes: Role of Versatile Ligands

Paola Nava (1) , Hervé Clavier (1) , Yves Gimbert (2) , Laurent Giordano (1) , Gérard Buono (1) , Stéphane Humbel (1)

1 ISM2 - Institut des Sciences Moléculaires de Marseille
2 DCM - Département de Chimie Moléculaire

Whereas the reaction of norbornadiene with terminal alkynes in presence of a phosphapalladacycle catalyst yields to the formation of hydroalkynation products, the use of phosphinous acid-phosphinito-containing palladium complexes gave rise to formal [2+1] cycloadducts. An experimental and computational approach was employed to study the mechanisms of the palladium-promoted hydroalkynation and [2+1] cycloaddition. On the one hand, experiences highlighted the crucial role of acidolysis steps on the catalytic activities. On the other hand, DFT calculations demonstrated the specificity of the phosphinito-phosphinous acid ligands, that is the non-equivalence of the two phosphorus atoms but the interchangeability of their properties. These results may have important implications for the mechanism of other palladium-catalyzed transformations especially those involving phosphapalladacycles and phosphinous acid-phosphinito-containing palladium complexes.

Mots clés: C-C coupling, computational chemistry, homogeneous catalysis, P ligands, palladium

Domaines: Catalyse; Chimie de coordination; Chimie organique; Chemo-informatique

Paola Nava, Hervé Clavier, Yves Gimbert, Laurent Giordano, Gérard Buono, et al.. Chemodivergent Palladium-Catalyzed Processes: Role of Versatile Ligands. ChemCatChem, 2015, 7 (23), pp.3848-3854. ⟨10.1002/cctc.201500809⟩. ⟨hal-01409758⟩