[2+1] Cycloaddition Affording Methylene-and Vinylidenecyclopropane Derivatives: A Journey around the Reactivity of Metal- Phosphinito-Phosphinous Acid Complexes

Hervé Clavier (1) , Gérard Buono (1)

1 ISM2 - Institut des Sciences Moléculaires de Marseille

Metal-phosphinito-phosphinous acid complexes are interesting catalysts exhibiting unique reactivities. In this account, we intend to provide a clear overview of palladium-and platinum-phosphinito-phosphinous acid complexes preparation starting from secondary phosphine oxides, and their applications in catalysis. They have been mainly used to develop [2+1] cycloadditions affording methylenecyclopropane derivatives using norbornenes and various alkynes as partners. As a function of the catalyst, the reaction conditions, or the nature of the reagents, different synthetic transformations have been observed: [2+1] cycloadditions giving rise to either alkylidenecyclopropanes or vinylidenecyclopropanes, tandem [2+1]/[3+2] cycloadditions… The mechanisms of these reactions have been studied to rationalize the different reactivities observed.

Domaines: Chimie de coordination; Chimie organique; Catalyse

Hervé Clavier, Gérard Buono. [2+1] Cycloaddition Affording Methylene-and Vinylidenecyclopropane Derivatives: A Journey around the Reactivity of Metal- Phosphinito-Phosphinous Acid Complexes . Chemical Record, 2017, 17 (4), pp.399-414. ⟨10.1002/tcr.201600081⟩. ⟨hal-01591163⟩