Catalytic reductive 4 + 1-cycloadditions of vinylidenes and dienes

Cycloaddition reactions provide direct and convergent routes to cycloalkanes, making them valuable targets for the development of synthetic methods. Whereas six-membered rings are readily accessible from Diels-Alder reactions, cycloadditions that generate five-membered rings are comparatively limited in scope. Here, we report that dinickel complexes catalyze 4 + 1-cycloaddition reactions of 1,3-dienes. The C1 partner is a vinylidene equivalent generated from the reductive activation of a 1,1-dichloroalkene in the presence of stoichiometric zinc. Intermolecular and intramolecular variants of the reaction are described, and high levels of asymmetric induction are achieved in the intramolecular cycloadditions using a C 2-symmetric chiral ligand that stabilizes a metal-metal bond.