Polymeric chiral crown ethers, 4. Substituent effects of methyl and phenyl groups in the 3,3′-positions on chiral recognition of poly(crown ether)s synthesized by cyclopolymerization of divinyl ethers derived from 1,1′-bi-2-naphthol

Chiral poly(crown ether)s were synthesized by cationic cyclopolymerization of (S)-2,2′-bis(2-vinyloxyethoxy)-3,3′-dimethyl-1,1′-binaphthyl [(S)- 1b ] and (R)-2,2′-bis[2-(2-vinyloxyethoxy)-ethoxy]-3,3′-dimethyl (or 3,3′-diphenyl)-1,1′-binaphthyl [(R)- 3b or (R)- 3c ]. The substituents in the 3,3′-positions of binaphthyl moiety disturb the intramolecular cyclization in the polymerization of monomer (S)- 1b , but have no influence on the cyclopolymerization tendency of monomers (R)- 3b and (R)- 3c . The polymers from (R)- 3b and (R)- 3c [(R)- 4b and (R)- 4c ] have a higher ability of chiral recognition towards a-amino acids, such as phenylglycine, phenylalanine, valine, and methionine, than the polymer from (R)- 3a [(R)- 4a ], which has no substituent in 3,3′-positions. The methyl and the phenyl substituents in the 3,3′-positions undoubtedly act as additional barrier causing an increase in the ability of chiral recognition, though the effect is less than expected from the result of model crown ethers.