NHC/Nickel(II)‐Catalyzed [3+2] Cross‐Dimerization of Unactivated Olefins and Methylenecyclopropanes

Abstract Cross‐dimerization of a methylenecyclopropane ( 1 ) and an unactivated alkene ( 2 ) with typical hydroalkenylation reactivity was observed for the first time by using a [NHC‐Ni(allyl)]BAr F catalyst (NHC=N‐heterocyclic carbene). Results show that the C−C cleavage of 1 did not involve a Ni 0 oxidative addition, which was crucial in former systems. Thus the method reported here emerges as a complementary method for attaining highly chemo‐ and regioselective synthesis of methylenecyclopentanes ( 3 ) with broad scope. An efficient NHC/Ni II ‐catalyzed rearrangement of 1 leads to the convergent synthesis of 3 in the presence of 2 .