2012 Fiscal Year Final Research Report

Development of Stereospecific Cationic Polymerizationthrough Intramolecular Participation at Polymer-end

Research Project

Project/Area Number	23655039
Research Category	Grant-in-Aid for Challenging Exploratory Research
Allocation Type	Multi-year Fund
Research Field	Organic chemistry
Research Institution	Kyoto University
Principal Investigator	YAMAGO Shigeru 京都大学, 化学研究所, 教授 (30222368)
Project Period (FY)	2011 – 2012
Keywords	立体規則性重合 / 立体選択的反応 / カチオン重合 / ラジカル重合
Research Abstract	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.