Development of Stereospecific Cationic Polymerizationthrough Intramolecular Participation at Polymer-end

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New monomers for the stereospecific cationic polymerization were designed and synthesized, and model reactions for the polymerization reaction were investigated. The monomer was designed to utilize intramolecular participation of the olefin-pendant group to the polymer-end cation, which would regulate the direction of an incoming monomer. The model reaction proceeded in good yield with >90% diastereoselectivity by an appropriate choice of the pendant group and Lewis acid used as an activator. The results suggest a new possibility for the control of stereoselectivity by using the polymer-end group, while the conventional method so far utilized steric effects of the penultimate group. The same concept was applied to the monomer design for the stereospecific radical polymerization, and a conditions for the extremely high (>99%) stereospecific radical polymerization was developed.