A Dinickel Catalyzed Cyclopropanation without the Formation of a Metal Carbene Intermediate.

(NDI)Ni2 catalysts (NDI=naphthyridine-diimine) promote cyclopropanation reactions of 1,3-dienes using (Me3 Si)CHN2 . Mechanistic studies reveal that a metal carbene intermediate is not part of the catalytic cycle. The (NDI)Ni2 (CHSiMe3 ) complex was independently synthesized and found to be unreactive toward dienes. Based on DFT models, we propose an alternative mechanism that begins with a Ni2 -mediated coupling of (Me3 Si)CHN2 and the diene. N2 extrusion followed by radical C-C bond formation generates the cyclopropane product. This model reproduces the experimentally observed regioselectivity and diastereoselectivity of the reaction.