[2+1] Cycloaddition Affording Methylene‐ and Vinylidenecyclopropane Derivatives: A Journey around the Reactivity of Metal‐Phosphinito–Phosphinous Acid Complexes. Issue 4 (6th October 2016)

• Record Type: Journal Article
• Authors: Clavier, Hervé; Buono, Gérard
• Is Part Of: Chemical record. Volume 17:Issue 4(2017)
• Page Start: 399
• Page End: 414
• Publication Date: 2016-10-06
• Subjects: cycloaddition, palladium, platinum, structure–activity relationships, synthesis design; Chemistry -- Periodicals; 540
• DOI: 10.1002/tcr.201600081
• Languages: English
• ISSNs: 1527-8999

Abstract

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. Abstract : Unpredictable outcomes : The preparation of alkylidenecyclopropanes and vinylidenecyclopropanes by [2+1] cycloaddition using metal‐phosphinito–phosphinous acid promoted catalysis and the associated reactivities of these useful synthons are presented.