Preparation of Vinylcyclopropanes by Sodium Mediated Reductive Isomerization of Methylenecyclopropanes

Karel Le Jeune (1) , Sabine Chevallier-Michaud (1) , David Gatineau (1) , Laurent Giordano (1) , Alphonse Tenaglia (1) , Hervé Clavier (1)

1 ISM2 - Institut des Sciences Moléculaires de Marseille

We disclosed therein a new reaction of reductive isomerization of methylenecyclopropanes (MCPs) to vinylcyclopropanes (VCPs). On treatment with sodium metal in liquid ammonia, MCPs bearing a C−O bond at allylic position undergo both a reductive cleavage of the C−O bond and an isomerization of the C−C double bond giving rise to VCPs. The scope of the reductive isomerization was investigated and showed a broad applicability since various functional groups are tolerated. MCP substrates were straightforwardly prepared by a palladium-promoted [2 + 1] cycloaddition between norbornene derivatives with alkynes.

Domaines: Chimie; Catalyse; Chimie organique

Karel Le Jeune, Sabine Chevallier-Michaud, David Gatineau, Laurent Giordano, Alphonse Tenaglia, et al.. Preparation of Vinylcyclopropanes by Sodium Mediated Reductive Isomerization of Methylenecyclopropanes. Journal of Organic Chemistry, 2015, 80 (17), pp.8821-8829. ⟨10.1021/acs.joc.5b01205⟩. ⟨hal-01409710⟩