Synthesis And Catalytic Properties Of Bidinaphthyl Chiral Covalent Organic Frameworks

Covalent organic frameworks（COFs）are a kind of new crystalline porous materials formed by the organic building units connected by covalent bonds.COFs have many advantages such as inherent porosity,low density,high surface area and excellent stability.They have shown broad applications,especially in the field of catalysis.Chiral COFs have great value in many fields such as asymmetric catalysis,chiral recognition and chiral separation due to their chiral properties.This thesis studies the synthesis of chiral COFs and its application in heterogeneous asymmetric catalysis.The research contents are mainly divided into the following two parts:1.Chiralα-amino phosphonate esters can be used as antibiotics,antibacterial drugs and anti-HIV drugs,which have attracted wide attention in modern pharmaceutical chemistry.Based on this,a simple and efficient method for preparingα-amino phosphonate esters was designed.A chiral COF（R-TPBBP-COF）was constructed from a chiral phosphoric acid derived building block（R）-BINOLPA-DA and 1,3,5-tris（4-aminophenyl）benzene（TAPB）.The chiralα-aminophenate was synthesized by the hydrophosphine acylation of benzaldehyde,amines and diethyl phosphite.The yield was up to 98%and the enantioselectivity was 94%.In addition,the catalyst still showed excellent stereoselectivity after 5 runs.highlighting the potential practicability of（R）-TPBBP-COF as asymmetric catalysts.2.Optically active propargyl alcohol is a precursor for the synthesis of many chiral organic compounds.Based on this,a chiral COF（R-BABINOL-TP-COF）was prepared using the chiral diamine building unit derived from Binnaphthalene（BINOL）（R）-BABINOL and 2,4,6-trialdehyde resorcinol（TP）.The hydroxyl group of the（R）-BABINOL-TP-COF)was combined with Ti（OⁱPr）₄ to form Lewis acid,which could catalyze the asymmetric addition reaction of phenylacetylene,benzaldehyde and diethylzinc to directly synthesize chiral propargyl alcohol.The catalyst showed high catalytic activity and enantioselectivity,and the catalytic performance remained good after five times of reuse.