title: [2+1] Cycloaddition Affording Methylene- and Vinylidenecyclopropane Derivatives: A Journey around the Reactivity of Metal-Phosphinito-Phosphinous Acid Complexes.
abstract: 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, their preparation from secondary phosphine oxides, and their applications in catalysis. They have been mainly used to develop [2+1] cycloadditions to afford 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, and so forth. The mechanisms of these reactions have been studied to rationalize the different reactivities observed.
authors.affiliation: Aix Marseille University, CNRS, Centrale Marseille, iSm2, Marseille, France.
authors.forename: Hervé
authors.initials: H
authors.lastname: Clavier
authors.affiliation: Aix Marseille University, CNRS, Centrale Marseille, iSm2, Marseille, France.
authors.forename: Gérard
authors.initials: G
authors.lastname: Buono
keywords: cycloaddition, palladium, platinum, structure-activity relationships, synthesis design