Enantio‐ and stereoselective cyclopolymerization of hexa‐1,5‐diene was achieved by enantiomerically pure dichloro zirconium(IV) pre‐catalysts 2 possessing chiral OSSO]‐type bis(phenolate) ligands (?)‐ 1 and (+)‐ 1 in combination with dried methylaluminoxane (dMAO) as an activator. The corresponding activities were recorded with quite high values up to 1,960 g mmol( 2 )–1 h–1, which are extremely larger than those of the related complexes. The microstructure analysis for the PMCPs furnished by pre‐catalysts (Λ,S,S)‐ 2 and (Δ,R,R)‐ 2 showed good isotacticity factors (α = 75?78%) and relatively high proportions of trans‐cyclopentane rings (σ = 14?21%). These enantiomeric PMCPs exhibited large specific optical rotations (α]D = +28 to +32° from (Λ,S,S)‐ 2 , ?26 to ?34° from (Δ,R,R)‐ 2 ).
