C-H Bond Activation Enables Rapid Access To Important Functional Molecules Such As Organophosphorus Compounds And Ortho-substituted Perylene Diimide Derivatives

C-H bond activation has developed into an indispensable strategy in the synthetic chemists' toolbox,and is exploited boundlessly.Focusing on C-H bond activation,this dissertation starts from development of new methods,synthesis of novel compounds and exploition of unique properties.On the one hand,substrates containing heteroatoms such as phosphorus coordinate strongly with metal catalysts.This coordination,which can lead to catalyst poisoning and deactivation,limits the application of C-H activation reactions catalyzed by metal.Therefore,the poisonous trouble of substrates to metal needs to be solved urgently;On the other hand,C-H bond activation shows obvious advantages in late-stage diversification of functional molecules.They still face the challenges of poor reaction selectivity and low reaction efficiency.This thesis aims to solve these two problems,and consists of the following six chapters:Chapter ?:The development status and problems of C-H bond activation were summarized.And the subject design of this thesis is proposed.Chapter ?:We developed an efficient and general approach for the synthesis of C3-phosphoindoles starting from N-sulfonylindoles and H-phosphine oxides.Several mild oxidants,such as AgNO3,di-tertbutyl peroxide(DTBP),and K2S2O8,could be used to promote this transformation.A free radical process may be involved in this reaction.Chapter ?:Using silver salts as oxidant or through electrochemically,we realized an Rh(?)-catalyzed aryl C-H phosphorylation reaction.We investigated the mechanism of overcoming the deactivating effect of phosphorus reagents,and demonstrated that Ag2CO3 has a dual role.Ag2CO3 or anodic oxidation effectively promotes reductive elimination,and the reaction experienced a hypervalent rhodium process.Chapter ?:We developed a novel S3·--triggered stitching thienannulation approach for the rapid construction of RDI-fused,largely ?-extended thienoacenes from alkyne-linked ?-systems with the strategy of multiple C-H bond activation.Furthermore,we investigated the physical properties of the newly formed thienoacenes,which revealed that these RDI-fused thienoacenes are promising candidates for highperformance organic semiconductors.Chapter ?:We studied the self-assemble of two comparable perylenediimide(PDI)dyads(PEP and PBP)with linkers of different length and developed a new host-guestlike aggregation strategy.With this strategy,PEB and PBP can selectively embrace each other through extended ?-? interactions to form PEP-PBP dimers.Further characterization shows that this PEP-PBP dimers assembly has special advantages in chiral recognition and so on.Chapter ?:Summary and outlooks of this dissertation.