Chiral arylnickel complexes as highly active initiators for screw‐sense selective living polymerization of 1,2‐diisocyanobenzenes

Optically active chiral organonickel complexes served as efficient chiral initiators for living aromatizing polymerization of 1,2‐diisocyanobenzene derivatives, which afford optically active helical poly(quinoxaline‐2,3‐diyl)s up to 84% s.e. (screw‐sense excess). In comparison with asymmetric polymerization with the corresponding organopalladium initiators, the nickel initiators show a much greater polymerization rate, while the selectivity remains high. The organonickel initiators can be generated in situ from nickel(0) precursors with the corresponding enantiopure ( S , S )‐2‐(4,5‐diphenylimidazolin‐2‐yl)phenyl chloride, leading to the convenient synthesis of highly stereo‐controlled poly(quinoxaline‐2,3‐diyl)s.