Metalated Porous Organic Ligand Polymer As Catalysts For The Synthesis Of Isoindolinones And Selective Hydrosilation,Hydrogermanation And Carboration Of Allenes

As the chemical industry has brought strong assistance to the economy and technology,many fields have also been comprehensively developed,but at the same time,it is also facing the problem of increasingly serious environmental pollution.The development of efficient catalysts is an effective way to solve environmental problems.Since catalysts play an extremely important role in contemporary chemical production,they are an important way to achieve high atomic economy.Porous organic polymers（POPs）,as a new type of carrier for heterogeneous catalysts,are a class of multifunctional materials with high specific surface area,rich pore structure,low skeleton density and good thermal stability.Pops materials can be rationally designed and modified with specific functional sites to modulate the electronic effects and steric structure of catalysts,thus effectively regulating the yield and selectivity of target products.Therefore,based on the porous organoligand polymer as the platform,while combing the design concept of homogeneous catalysts and the advantages of heterogeneous catalysts,the metal/porous organoligand polymer is applied to the synthesis of isoindolinone compounds to achieve high regioselectivity and stereoselectivity of allenes hydrosilylation,hydrogermanation and carboboration.We hope to further study the catalytic mechanism at the atomic-molecular level,condense the key factors controlling the catalytic performance,and guide the development of efficient and cheap new catalytic systems.（1）Isoindolinone is an important structural unit,which has a wide range of biological activities,such as antibacterial,antitumor,anxiety.We have developed a series of isoindolinones synthesized in moderate to excellent yields using commercially available o-bromobenzaldehyde and isonitrile as substrates and Pd/POL-PPh₃ as a multiphase catalyst via oxidative addition of metallic palladium,double insertion of isonitrile,and intramolecular cyclization.The enrichment of polymer pores can effectively enrich o-bromobenzaldehyde and promote the synthesis of isoindolinones.It also utilizes the cyclic catalysis of POL-PPh₃,and tis catalytic activity did not change significantly after 3 times of use.This strategy effectively solves the problems of difficult separation,recovery and reuse of homogeneous catalyst,and has the potential of industrial development.This strategy eliminates the need for substrate prefunctionalization and has the advantages of high atomic economy and simplicity of operation.（2）α-Allylsilicon compounds have the characteristics of low toxicity and stability,and are valuable intermediates in organic synthesis transformations for coupling and cycloaddition reactions.However,Since the allene has two mutually perpendicularπ-orbitals,making the electron cloud density of the three carbon atoms in the two carbon-carbon double bonds less different,the unique reaction properties cause the metal to be difficult to identify at a fixed point,resulting in six different conformations of target products for this type of reaction,thus controlling its regioselectivity and stereoselectivity is a challenging topic.We synthesized porous organic polymers with triphenylphosphorus ligands as the skeleton,and obtained the single-atom palladium porous organophosphine ligand polymer catalyst Pd₁@POL-5 by a simple"metal-ligand exchange method",and achievedα-region selective hydrosilylation of allenes to obtain highly selectiveα-allylsilanes.The monoatomic palladium porous organophosphine ligand polymer catalyst Pd₁@POL-5 has high catalytic activity with no significant decrease in catalytic activity after 10 cycles in a flow chemistry device,while achieving trace catalysis of organic chemical reactions with TON value as high as 772358,which is promising for industrial applications.In this chapter Pd₁@POL-5catalyst,the porous organophosphine ligand polymer not only acts as a ligand but also as a carrier for the metal,and can further improve the selectivity of the reaction by altering the electronic groups on the triphenylphosphine ligand backbone and thus fine-tuning the properties of the metal and enhancing the recognition of the active site of the allene by the catalyst.（3）α-Allylgermanium compounds are important intermediates in organic synthesis and exhibit ultra-high reactivity in electrophilic substitution reactions and cross-coupling reactions,which are crucial for the construction of complex molecular structures.At present,the synthesis methods ofα-allylgermanium compounds usually use metals or lewis acids as catalysts,but the regioselectivity and stereoselectivity of this method are not high,and a mixture of allylgermanium compounds and alkenylgermanium compounds is usually obtained.Therefore,we constructed metalized porous organophosphine ligand polymer catalysts with high specific surface area,multistage pore channels and good stability to achieve hydrogermanation of electronically unbiased allenes to obtain highly regioselectiveα-allylgermanium compounds（r.r.>100:1）.Among them,porous organic polymers are synthesized by free radical self-polymerization.This strategy increases the steric hindrance of phosphorus coordination sites through the building blocks of rigid molecules of benzene rings,which is beneficial to overcome thermodynamic effects and enhance the recognition of allene functional groups.This strategy has the advantages of high efficiency,environmental friendliness,mild reaction conditions,high atomic economy and wide substrate applicability.（4）β-Z-Alkenylborates are a kind of compounds with unique stability and non-toxicity,and have important applications in the field of small molecule drugs and functional polymeric materials.In the previous allenes carboborylation,prefunctionalization of the allene is usually required,leading to a limited range of substrates and to allyl boronic acid ester compounds and allyl boronic acids mixtures,so the selectivity of electronically unbiased allenes carboborylation reactions has not been addressed.In this chapter,we found that the selectivity of the reaction is controlled by the metal and ligand synergistically by analyzing the mechanism of the carbonboration.In this chapter,a series of metal-copper carbine-ligand polymer catalysts Cu/POL-n were obtained by synthesizing porous organic polymers with monodentate and bidentate carbene ligands as the core skeleton,ligated with copper acetate,and successfully catalyzed electronically unbiased allenes carboborylation to obtain highly regioselective and stereoselectiveβ-Z-alkenylborates compounds（r.r.>100:1）.Among them,the vinyl group will undergo carbon chain lengthening by means of radical self-polymerization.This strategy not only makes the spatial site resistance of the porous organic polymer carbinol ligand larger,but also provides abundant coordination sites,effectively inhibits metal agglomeration,enhances catalyst activity,and finally realizes the carboborylation of the allene.