Palladium-Catalyzed [2+1] Cycloadditions Affording Vinylidenecyclopropanes as Precursors of 7-Membered Carbocycles

Aymeric Lepronier (1) , Thierry Achard (1) , Laurent Giordano (1) , Alphonse Tenaglia (1) , Gérard Buono (1) , Hervé Clavier (1)

1 ISM2 - Institut des Sciences Moléculaires de Marseille

Palladium(II) acetate in association with secondary phosphine oxides provides an efficient catalytic system for [2+1] cycloadditions starting from oxanorbornene derivatives and tertiary propargyl esters giving rise to vinylidenecyclopropanes. This reaction is specific to bidentate phosphinito-phosphinous acid ligands generated from secondary phosphine oxides. The [2+1] cycloaddition was found broad in scope with a high tolerance to various functional groups. Moreover, vinylidenecyclopropanes were straightforwardly converted into oxabicyclo[3.2.1]oct-2-ene derivatives through a palladium-catalyzed ring-expansion. Finally, the oxa bridge cleavage of oxatricyclic compounds allows the obtention of functionalized 7-membered carbocycles.

Mots clés: Carbocycles; Cycloaddition; Palladium; Vinylidenecyclopropane; Secondary Phosphine Oxide

Domaines: Catalyse; Chimie organique

Aymeric Lepronier, Thierry Achard, Laurent Giordano, Alphonse Tenaglia, Gérard Buono, et al.. Palladium-Catalyzed [2+1] Cycloadditions Affording Vinylidenecyclopropanes as Precursors of 7-Membered Carbocycles. Advanced Synthesis and Catalysis, 2016, 358, pp.631 - 642. ⟨10.1002/adsc.201500971⟩. ⟨hal-01409737⟩