Heterogenization of homogeneous catalysts combine the high activity and selectivity of homogeneous catalysts and the stability and ease of separation of heterogeneous catalysts. Single-Atom Catalysts (SACs) provide an alternative for heterogenization of homogeneous catalysts and act as a bridge between homogeneous and heterogeneous catalysis. Porous Organic Polymers (POPs) are one of these novel methods of SACs and have the structural feature-high specific surface area, excellent stability, good robustness and swelling, which could help isolated active sites dispersed on the supporting materials as homogeneous catalysis.
This thesis aims at designing and synthesizing a series of POPs and utilizing these POPs in asymmetric catalysis. Nine POPs which are based on 2,2'-bipyridine, (R)-BINAP and (R)-MEO-BIPHEP, have been synthesized. BPY-POPs-1 was applied in direct C-H borylation of arenes. BINAP-POP-5 was investigated for asymmetric α-arylation of ketones with chloroarenes. The Ni-BINAP-POP catalyst displayed excellent activity and high enantioselectivity, which was same as homogeneous catalyst. The POP-5 could be reuse for three times without any loss in enantioselectivity. The combination of BINAP-POP-6 with Cu(OAc)2 realized the asymmetric hydrosilylation of ketones with excellent activity (up to 100%) and high enantioselectivity (up to 99%). BINAP-POP-6 can be recycled for three times without any obvious loss in activity and enantiioselectivity. These results highlight the potential of POPs in future catalysis.