Retention or Inversion in Stereospecific Nickel-Catalyzed Cross-Coupling of Benzylic Carbamates with Arylboronic Esters: Control of Absolute Stereochemistry with an Achiral Catalyst

Stereospecific coupling of benzylic carbamates and pivalates with aryl- and heteroarylboronic esters has been developed. The reaction proceeds with selective inversion or retention at the electrophilic carbon, depending on the nature of the ligand. Tricyclohexylphosphine ligand provides the product with retention, while an N-heterocyclic carbene ligand provides the product with inversion.