Synthesis and asymmetric polymerization of chiral maleimides bearing an aza crown ether

• Published in: Polymer journal Vol. 43; no. 3; pp. 279 - 284
• Main Authors: AZECHI, Motohisa, IWAI, Jun, YAMABUKI, Kazuhiro, ONIMURA, Kenjiro, OISHI, Tsutomu
• Format: Journal Article
• Language: English
• Published: Avenel, NJ Nature Publishing Group 01.03.2011
• Subjects: Amino acids; Applied sciences; Asymmetry; Bearing; Crown ethers; Derivatives; Exact sciences and technology; Optical properties; Optical rotation; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; Substituent effect; asymmetric polymerization; Optically active polymer; Nitrogen crown compound; amino acid; Oxazoline derivatives; Chiral compound; Sparteine; Experimental study; Asymmetric induction; Lateral group; Free radical polymerization; Lithium Organic compounds; maleimide; Preparation; Optical activity; Maleimide derivative polymer; Carboxamide; Anionic polymerization; Stereoelective polymerization; Crown compound polymer; aza crown ether
• ISSN: 0032-3896; 1349-0540
• DOI: 10.1038/pj.2010.139

Chiral N-substituted maleimide derivatives bearing L-phenylalanine- or L-leucine-introduced aza crown ether ((S)-A15C5PAMI, (S)-A15C5LMI) were synthesized from maleic anhydride, corresponding amino acids and aza crown ether, and polymerized with an organometal/chiral ligand. The number-average-molecular weights and the specific optical rotations of the polymers were 700-5600 and -105.8° to -38.3°, respectively. The specific optical rotations of all polymers tended to a positive direction, compared with model compounds ((S)-A15C5PASI ([α]435 =-218.1°), (S)-A15C5LSI ([α]435 =-215.1°)). Asymmetric inductions in the main chains of the polymers were investigated by the measurements of specific optical rotation, circular dichroism.