Intermolecular C(SP3)-H Bond Insertion Reaction Of Sulfonyl Hydrazone Catalyzed By Metallic Porphyrin

This thesis mainly focusesonthe carbene transfer reactionscatalyzed by iridiumporphyrins,which synthesizedbyiridium complexes and meso-tetra-substituted porphyrins.The main body is divided into three parts:1).The synthesis of fivedifferent types of meso-tetra-substituted porphyrinsas well as the corresponding metal porphyrinsby the reported synthesis methods;2).The C-H bond insertion reaction of sulfonyl hydrazone to the N-methyl group of N-methyl compounds by iridium porphyrin complexes as catalysts.In the firstpart,four meso-tetra-substituted porphyrins were synthesized by condensation of substituted benzaldehyde and pyrrole in 15%～35%yields.In addition,a chiral porphyrin H₂（（-）-D₄*-por）was synthesized by Halterman reported 8-steps method（total yield:0.6%）.Then six iridium porphyrin complexes were synthesized by complexation of porphyrins and various metal precursors（e.g.[Ir（cod）Cl]2）.What’s more,modification by axial ligands were studied on two kinds of iridium porphyrin complexes（[Ir（TTP）（CO）Cl]and[Ir（（-）-D₄*-por）（CO）Cl]）.As a result,the corresponding two kinds of methyl iridium porphyrin complexes（[Ir（TTP）（Me）]and[Ir（（-）-D₄*-por）（Me）]）have been obtained.In the second part,the intermolecular Carbin C（sp³）-H bond insertion reaction involving arylketone sulfonyl hydrazone was first realized using iridium porphyrin[Ir（TTP）（Me）].[Ir（TTP）（Me）]can effectively achieve arylketone sulfonyl hydrazone to aromatic amine compounds Carbin C-H bond insertion reaction,the highest separation yield of 82%.We have also attempted to use chiral iridium porphyrins[Ir（（-）-D₄*-Por）（Co）Cl]and[Ir（（-）-D₄*-Por）（Me）]for the initial exploration of asymmetric insertion reactions,but unfortunately did not achieve.The reaction mechanism was speculated based on the experiment of free radical capture.