A new type of asymmetric chirogenic polymerization by asymmetric allylic substitution catalyzed by planar–chiral ruthenium complexes was designed. The polymerization systems function in a highly stereoselective manner. The asymmetric carbon in the main chain is precisely controlled. Each monomer unit of the polymer has a potentially reactive terminal olefin, which can be used for further transformations, ring-closing metathesis and thiol–ene reaction. Additionally, the resulting polymer can be transformed poly “arylopeptide”, through reductive cleavage of the N–O bond in N-alkoxyamide, which adopts a one-handed stable helical conformation in solution.
