L-proline functionalized pH-responsive copolymers as supported organocatalysts for asymmetric aldol reaction in water

Abstract

pH-Responsive copolymers with reversible transformation ability have been investigated as new effective carriers for L-proline to catalyze asymmetric aldol reaction in water. A series of block copolymers of mPEG-b-P(DEAx-co-L-ProlAy) (mPEG-PDL) bearing L-proline catalytic sites and pH-responsive poly (diethylaminoethyl methacrylate) (PDEA) segments were synthesized by the reversible addition-fragmentation chain transfer (RAFT) polymerization in the presence of methyl polyethylene glycol (mPEG) trithiocarbonate macro-RAFT agent. The pH-induced self-assembly behaviors of three copolymer catalysts with different contents of PDEA were investigated via the combination of UV–visible spectrometer (UV–vis), dynamic light scattering (DLS) and transmission electron microscopy (TEM). Catalytic activity and stereoselectivity of these copolymer catalysts were evaluated by direct asymmetric aldol reaction of p-nitrobenzaldehyde and cyclohexanone in water. The results indicated that catalytic activity and stereoselectivity effected by the pH value of aqueous solution and the structures of copolymer catalyst assemblies. mPEG-PDL-2 give the aldol product with high conv., yield, anti/syn, and ee (92%, 91%, 92/8, 96%), respectively at pH 7.0. Furthermore, these pH-responsive copolymers supported L-proline are easily recycled by a reversible phase transition.