Regioselective Palladium-Catalyzed Allylation of Fulvenes

Article abstract of DOI:10.1016/S0040-4020(01)80737-7

Fulvene-anions (vinyl cyclopentadienyl anions) are exclusively allylated in the exocyclic position by allylic chlorides, allylic acetates, and allylic carbonates in the presence of catalytic amounts of bis(dibenzylideneacetone)palladium(0) and triphenyl phosphine in good to excellent yield.A high degree of regioselectivity is observed with regard to the allylic substrate, and the most hindered position was predominately substituted.Inversion of stereochimistry of the allylic carbon by migration of the anion from the metal, of an intermediate η³-allylpalladium complex, to carbon is observed.