Switch in Selectivities by Dinuclear Nickel Catalysis: 1,4-Hydroarylation of 1,3-Dienes to Z -Olefins.

One of the most challenging tasks in organic synthesis is to control selectivities, especially switching the well-known selectivity to obtain new isomers that were previously inaccessible. Inspired by biological catalysis involving multiple metal centers, catalysis enabled by binuclear metal complexes offers the potential to induce reactivity and selectivity that might not be available to mononuclear catalysts. Herein, we describe that using a macrocyclic bis pyridyl diimine dinickel complex as the catalyst, the commonly observed 4,3-regioselectivity of hydroarylation of 1,3-dienes is switched to 1,4-hydroarylation with thermodynamically less stable Z -stereoselectivity, offering challenging synthetic target Z -olefins. DFT calculations show that the activation of 1,3-diene proceeds through dinuclear Ni-diolefin coordination, and the synergistic effects of two Ni nuclei enable reactivity and selectivity of this binuclear catalysis substantially different from those of mononuclear nickel complexes in the current reaction.