Studies on systhesis, structure, and chiral recognition ability of helical, optically active polymers

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1. Optically active, helical polymers were successfully synthesized from novel methacrylates, acrylates, and acrylamides. Diphenyl-3-pyridylmethyl methacrylate, phenyl-bis (2-pyridyl) methyl methacrylate, 1-phenyldibenzosuberyl methacrylate, and 1- (2-pyridyl) dibenzosuberyl methacrylate gave almost perfectly isotactic, one-handed helical polymers through anionic polymerization using the complex of N,N'-diphenylethylenediamine monolithium amide with (+) -1- (2-pyrrolidinylmethyl) pyrrolidine. Helix-sense-selective polymerization of the latter two monomers was realized also through radical mechanism using optically active transfer agents and solvents.2. Optically active polymers were obtained from aromatic isocyanates. Polymerization of m-methylphenyl and m-methoxyphenyl isocyanates with (+) -1- (2-methoxymethyl) pyrrolidine monolithium amide gave optically active polymers having single-handed helical structure in excess. It was clarified that these polymers have one-handed helical part extending from the alpha-end to the chain length corresponding to 12-13 monomeric units and thereafter, helix reversal takes place.3. Novel phenylacetylene derivatives bearing chiral carbamate groups in the side chain gave optically active, helical polymers by homopolymerization and copolymerization with archiral monomers using Rh catalysts. The polymers resolved many racemic compounds when used as a chiral packing material for HPLC.