The Synthesis Of Polymers Derived From BINOL And Preliminary Application Of The Polymer In Asymmetric Catalysis

1,1’-Binaphthol(BINOL)has been studied by chemists because of its easy to modify multiple chiral sites.Chiral binaphthol has a unique chiral structure and is widely used in various organic asymmetric reactions with excellent results.With the deepening of research,many polymers based on binaphthol have been studied and used to catalyze asymmetric synthesis.Relative to small molecules,the products of the polymer-catalyzed asymmetric reaction are easy to separate,have little impact on the environment,and can be recycled by simple filtration.Therefore,the use of the polymer bearing dinaphthol to catalyze the asymmetric reaction has become a hot spot.We designed and synthesized some macromolecular ligands derived from chiral BINOL.In order to investigate its catalytic performance,we have applied the obtained macromolecular ligand to the asymmetric epoxidation reaction of(E)-α,β-unsaturated aromatic ketone and the asymmetric addition reaction of aldehyde.(1)We have recently reported the synthesis of poly[(S)-3-acrylamide-2,2’-dihyd-roxy-1,1’-binaphthy-l] and its application in the asymmetric addition of diethylzinc to aromatic aldehydes.The synthesis route of poly[(S)-3-acrylamide-2,2’-dihyd-roxy-1,1’-binaphthy-l] is shown in Figure 1.We hope to develop more applications of this polymer.In this paper,a type of reusable chiral polymer BINOL ligand was chelated with diethyl zinc to give a self-loading chiral catalyst.This polymer-supported chiral catalyst had been applied in asymmetric epoxidation of(E)-α,β-unsaturated aromatic ketone.The reaction conditions were optimized and the substrates were extended.Further,this polymer-supported chiral catalyst was recycled and reused after the reaction.(2)Polymerization of(S)-3,3’-amino-2,2’-dihydroxy-1,1’-binaphthalene with(S)-3,3’-dimethyl-2,2’-dimethoxymethoxy-1,1’-binaphthalene was performed by aminoaldehyde condensation and the obtainedpolmer was applicated in catalytic asymmetric addition of diethylzinc to alde.After the optimization of the conditions,relatively good reaction conditions were obtained,and the universality of the substrate was studied.