DFT Study of Mechanism and Stereochemistry of Nickel-Catalyzed trans -Arylative Desymmetrizing Cyclization of Alkyne-Tethered Malononitriles.

Present here is a density functional theory (DFT) study of the mechanism and origin of enantioselectivity of Ni-catalyzed desymmetric cyclization of alkyne-tethered malononitriles and aryl boronic acids. The reaction starts from transmetalation and arylnickel addition, followed by trans to cis isomerization to give cis -alkenyl nickel species. The stereodetermining step is the CN insertion, which prefers a transition state with the bystander CN group staying away from the ligand to reduce steric repulsion, and gives the final ( R )-product.