Probing the Mechanism of Ni-Catalyzed Asymmetric Reppe Carbonylation of Cyclopropenes with CO and ROH

There is ongoing intense interest in catalysis with the Earth-abundant metal nickel. This DFT study reveals a plausible mechanism for the first Ni-catalyzed asymmetric Reppe carbonylation of cyclopropenes with carbon monoxide and phenols/alcohols. The RO-H bond undergoes a distinct heterolytic cleavage rather than the proposed oxidative addition, transferring a proton to a nickel-bound anionic carbon atom in a stereoselective manner. This and other novel insights gained can have implications for developing new asymmetric Reppe reactions.