Synthesis Of Functional Chiral Ordered Mesoporous Polymers For Heterogeneous Organocatalysis

Owing to their uniform and tunable mesoporous pore size,large specific surface area,and enhanced hydrothermal and mechanical stabilities,easy functionalization at the molecular level,ordered mesoporous polymers have recently received significant attention.Especially,because the main skeletons of ordered mesoporous polymers are composed of bezene rings,it is easy to functionalize these materials via chemical modification.These advantages make ordered mesoporous polymers serve as ideal solid platforms for heterogeneous catalysis.Nevertheless,to date,only limited works have been documented on the utilization of ordered mesoporous polymers for heterogeneous catalysis,and to the best of our knowledge,no example has been reported concerning the application of ordered mesoporous polymers in heterogeneous asymmetric catalysis.In this context,the synthesis of organocatalysts-functionalized chiral ordered mesoporous polymers for heterogeneous asymmetric organocatalysis will be a promising and challenging research area.Accordingly,the main contents of this thesis are the synthesis and characterization of the organocatalysts-functionalized chiral ordered mesoporous polymers,and utilization them for the heterogeneous asymmetric organocatalysis.And the main achievements could be divided into the following three parts:1.We first modified the ordered mesoporous polymer FDU-15 with chlorosulfonic acid,and then an organocatalyst,chiral cyclohexanediamine,was loaded to the pores of FDU-15 through the ionic bonding cooperation.The chiral cyclohexanediamine functionalized mesoporous polymer exhibits high ordered mesoporous porosities,and could be applied to catalyze the asymmetric Aldol reaction of cyclohexanone to aromatic aldehydes.The heterogeneous catalyst shows high catalytic activity(> 99% yield)and high enantioselectivity(97% ee),which is comparable with its homogeneous counterpart.Furthermore,the solid catalyst can be reused for at least six times with no obvious decrease of activities and enantioselectivities.2.Using a similar approach,another organocatalyst,Mac Millan catalyst,was loaded to the pores of FDU-15 through the ionic bonding cooperation.The obtained catalyst can be applied as an efficient catalyst for the asymmetric Diels-Alder reaction(95% yield,76% ee for exo,89% ee for endo).This solid catalyst can be reused for at least three times with no obvious decrease of activities and enantioselectivities.3.A chiral pyrrolidine based organocatalyst has been successfully loaded to the pores of FDU-15 through the ionic bonding cooperation,and the obtained polymer has been applied as a highly efficient heterogeneous organocatalyst for the asymmetric Michael addition(84% yield,89% ee).The further exploration of the catalytic performance of this solid catalyst is in proceeding.