Design,Synthesis And Asymmetric Catalytic Properties Of Chiral Crystalline Porous Materials Based On Spirobiindane

Chiral crystalline porous materials have received widespread attention due to their great potentials in asymmetric catalysis,chiral recognition and sensing,enantioselective separation and chiral optics,et.al.In this thesis,the carboxylate-fuctionalized ligands based on enantiopure 1,1'-spirobiindane-7,7'-diol skeleton were synthesized and assembly with metal ions to construct several novel metal-organic frameworks and hydrogen-bonded organic frameworks.The compositions and structures of these chiral crystalline porous materials were characterized by a variety of techniques including single crystal X-ray diffraction and their asymmetric catalytic properties were also explored.The thesis comprises the following five chapters:In Chapter 1,the research background of chiral crystalline porous materials was introduced,including the design,synthesis and structures of metal-organic frameworks and hydrogen-bonded organic frameworks,as well as their applications in asymmetric catalysis.In addition,the opportunities and challenges remained in this area were also discussed and presented.And last,the significance of the research topic and research progress were demonstrated.In Chapter 2,a tetracarboxyl-functionalized chiral ligand of H₄L₁ based on1,1'-spirobiindane-7,7'-diol was synthesized through ten step chemical reactions.By assembling with Zr⁴⁺ions,a chiral porous metal-organic framework 1 was successfully constructed under solvothermal condition.After post-synthetic modification of 1 with hexamethylphosphorous triamide?HMPT?and succedent post-metalation with Rh?COD?₂BF₄,the desired material 1-P?NMe?₂/Rh was shown to be highly efficient and recyclable heterogeneous catalyst for asymmetric hydrogenation of enamides.Through careful comparison of its catalytic activity with the corresponding homogeneous counterpart,the actual reactive species were demonstrated to be the mono-coodinated Rh-ligand complex.In Chapter 3,two tetracarboxyl-functionalized chiral ligands of H₄L₂ and H₄L₃based on 1,1'-spirobiindane-7,7'-phosphoric acid were synthesized through eleven step chemical reactions,respectively.After assembling with p-tert-butylsulfonylcalix[4]arenes?H₄TBSC?and Ni²⁺/Co²⁺ions,two types of chiral octahedral coodination cage based hydrogen-bonded organic frameworks 1-Ni/1-Co and 1-Co'were successfully prepared under solvothermal conditions.The exposed Br?nsted acidic phosphoric acid groups in HOFs 1-Ni and 1-Co can effectively catalyze asymmetric[3+2]cycloaddition reaction of indoles with quinone monoimine and Friedel-Crafts alkylation of indole with aryl aldimines with excellent enantioselectivities.The afforded enantioselectivities?up to99.9%ee?surpass those of the homogeneous counterparts and compare favorably with those of the most enantioselective homogeneous phosphoric acid catalysts reported to date.In Chapter 4,two tetracarboxyl-functionalized chiral ligands of H₄L₂ and H₄L₄ based on 1,1'-spirobiindane-7,7'-phosphoric acid were synthesized through eleven step chemical reactions,respectively.After assembling with Zr⁴⁺ions,two topologically isostructural chiral metal-organic frameworks Spiro-1 and Spiro-2 were successfully constructed under solvothermal conditions.The two highly porous materials shown great chemical stability and large specific surface areas.Significantly enhanced Br?nsted acidity was observed for the phosphoric acids that are uniformly distributed within the frameworks in comparison with the nonimmobilized acids.The uniformly distributed Br?nsted acidic phosphoric acid groups embedded in MOFs Spiro-1 and Spiro-2 make them highly efficient and recyclable solid catalysts for a variety of asymmetric organic transformations with enantioselctivities up to 99.9%.In addition,due to the coexistence of abundant Lewis acidic Zr sites,the two MOFs could also realize some asymmetric tandem reactions with apparently higher reactivity and enantioselectivity than the homogeneous controls.In Chapter 5,a briefly summary and further prospect of this thesis were given.