Chemodivergent Palladium-Catalyzed Processes: Role of Versatile LigandsReport as inadecuate

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

Abstract : 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.

Author: Paola Nava - Hervé Clavier - Yves Gimbert - Laurent Giordano - Gérard Buono - Stéphane Humbel -



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