Abstract

A highly bulky methacrylate, tris(trimethylsilyl)silyl or supersilyl methacrylate, was polymerized quantitatively with 9-fluorenyllithium in the presence of (−)-sparteine as a chiral ligand in toluene at −78 °C to give insoluble polymers. The obtained polymers exhibited high isotacticity (mm>99%) and chirality, which was confirmed by diffuse reflectance circular dichroism spectroscopy. Thus, the bulky silyl methacrylate undergoes asymmetric anionic polymerization with the chiral initiating systems via formation of a prevailing one-handed helical conformation.

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