Enantioselective CO₂ Fixation Via a Heck-Coupling/Carboxylation Cascade Catalyzed by Nickel

A novel asymmetric nickel-based procedure has been developed in which CO₂ fixation is achieved as a second step of a truncated Heck coupling. For this, a new chiral ligand has been prepared and shown to achieve enantiomeric excesses up to 99 %. The overall process efficiently furnishes chiral 2,3-dihydrobenzofuran-3-ylacetic acids, an important class of bioactive products, from easy to prepare starting materials. A combined experimental and computational effort revealed the key steps of the catalytic cycle and suggested the unexpected participation of Ni(I) species in the coupling event.