title: Synthesis of functional poly(phenyl isocyanide)s with macromolecular helicity memory and their use as asymmetric organocatalysts.
abstract: To develop a novel polymer-based asymmetric organocatalyst, a series of helical poly(phenyl isocyanide)s with functional pendant groups were prepared by modifying the side groups of the optically active helical poly(4-carboxyphenyl isocyanide) with a macromolecular helicity memory. Helical polyisocyanides partially modified with achiral amines, such as piperazine, maintained their chiral memory and enantioselectively catalyzed a direct aldol reaction. Although the enantioselectivity was low, the original helical poly(4-carboxyphenyl isocyanide) showed no catalytic activity. These results indicated that the macromolecular helicity of the modified polyisocyanides together with bifunctional amino and carboxy acid pendant residues arranged in a helical array along the polymer backbones plays an important role in the enantioselectivity.
authors.affiliation: Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya, Japan.
authors.forename: Toshitaka
authors.initials: T
authors.lastname: Miyabe
authors.forename: Yoko
authors.initials: Y
authors.lastname: Hase
authors.forename: Hiroki
authors.initials: H
authors.lastname: Iida
authors.forename: Katsuhiro
authors.initials: K
authors.lastname: Maeda
authors.forename: Eiji
authors.initials: E
authors.lastname: Yashima