Synthesis of Cinchona Alkaloid-Derived Chiral Polymers by Mizoroki–Heck Polymerization and Their Application to Asymmetric Catalysis

Abstract

To facilitate the asymmetric catalysis process, we designed novel polymeric chiral catalysts. Since quaternary ammonium salts of cinchona alkaloid derivatives show efficient catalytic activity in various asymmetric transformations, we have synthesized novel chiral polymer catalysts containing cinchonidinium moieties in the main chain of the polymer. Repetitive Mizoroki–Heck coupling reactions between the cinchona alkaloid-derived dimer and diiodide afforded the chiral polymer catalysts, which were subsequently used as catalysts in asymmetric benzylation reactions to yield the corresponding phenylalanine derivatives in higher yields and levels of enantioselectivity than can be obtained with a monomeric catalyst. Because of the insolubility of the polymeric catalysts, they were easily recovered from the reaction mixture and reused several times.