Synthesis and catalytic activity of the thermoresponsive polymers having pyrrolidine side chains as base functionalities

Optically active polymers having chiral 2‐aminomethylpyrrolidine side chains have been newly synthesized by a radical homopolymerization of the corresponding protected acrylamide monomer and copolymerization with N‐isopropylacrylamide followed by deprotection. The resulting polymers were found to be thermoresponsive showing lower critical solution temperatures (LCSTs) at 27–65°C in their aqueous solutions. The pyrrolidine side chains of the resulting thermoresponsive polymer promoted aldol reaction between cyclohexanone and p‐nitrobenzaldehyde in water, and the reaction proceeded most smoothly at its LCST. Moreover, the diastereomeric ratio (syn : anti) of the aldol adducts obtained at the reaction at 40°C was 22 : 78, whereas the diastereomeric ratio (syn : anti) was 55 : 45 at 20°C. These results indicate that the pyrrolidine side chains catalyze the aldol reactions in the relatively hydrophobic field generated by the thermoresponsive polymer at its LCST. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013