The importance of the Ni catalyst in achieving catalytic asymmetric Ni/Cr-mediated coupling reactions effectively is demonstrated. Six phenanthroline–NiCl2 complexes 1a–c and 2a–c and five types of alkenyl iodides A–E were chosen for the study, thereby demonstrating that these Ni catalysts display a wide range of overall reactivity profiles in terms of the degree of asymmetric induction, geometrical isomerization, and coupling rate. For three types of ...