Rational Design,Assembly and Properties of Chiral Functional Materials Based on TADDOL

Author:Wang Xiu Ren

Supervisor:cui yong


Degree Year:2016





Chiral porous materials,especially for chiral porous organic polymers(CPOPs)、chiral covalent organic framworks(CCOFs)and metal organic frameworks(MOFs)have attracted considerable attentions in gas adsorption,chemical sensing,asymmetric catalysis and separation.In this thesis,a series of TADDOL based functional organic bridging intermediates,including carboxylic acid ligand,bromo-and aldehyde group-compounds,were synthesized and further employed to build CPOPs、CCOFs and MOFs with robust structures and unique properties.These three kinds of materials were explored in the area of asymmetric catalysis and enantiomeric flurescence.The thesis includes the following six chapters.In Chapter 1,The research background is briefly introduced,including the rational design and synthetic approach of CPOPs,CCOFs and MOFs,as well as their applications in gas adsorption,asymmetric catalysis,chemical sensor and chiral recognition and separation.Then,the opportunities and challenges remained in this area are discussed.Finally,the overview of the thesis topic together with the research progress are presented.In Chapter 2,Two CPOPs were synthesized by linking a TADDOL-embedded building block(R,R)-a with arylethynylenes units.The CPOPs are highly stable to thermal treatment,moisture,acidity,and basicity.After being treated with Ti(OiPr)4,the CPOPs could be used as highly effective and reusable heterogeneous catalyst for asymmetric diethylzinc addition to aldehydes with up to 99%conversion and 95%ee.This result is almost comparable to that of the homogeneous TADDOL/Ti catalyst.In Chapter 3,Two aldehyde group-compounds b and c based on TADDOL blocks were designed and synthesized respectively,and further utilized to construct three CCOFs 1-2 by means of reversible covalent bond formation reactions.As catalysts,both CCOF-1/Ti and CCOF-2/Ti have the similar activity to catalyze the reaction of the asymmetric diethylzinc addition with up to 99%conversion and 95%ee.In Chapter 4,A carboxyl-functionallized TADDOL ligand H4L1 was designed and synthesized,and used to construct the homochiral 3D porous MOF 1 by coordinated with InCl3 under thermal solvothermal conditions.The flurescene of the MOF 1 was decreased by six enantiomeric saccharides in solution with enantioselectivity factors of 1.29-2.04.In Chapter 5,Three homochiral microporous MOF 2-4 were assembled from an axially C2-synmmetric TADDOL carboxyl-functionalized ligand H4L1 respectively.These three new MOF materials were stable structures and characterized by multiple spectroscopies.In Chapter 6,conclusion and outlook.