The Application Of Hypervalent Iodine Reagents In Constructions Of Aromatic Carbon-halogen Bond And Synthesis Of Nitrogen-containing Heterocycles

The main studies of this thesis are specific application of hypervalent iodine.One is hypervalent iodine mediated penyl isocyanides or vinyl isocyanides insertion with aromatic aldehydes toward nitrogen-containing heterocycles bearing building-block of phenanthridine and isoquinoline.Another is hypervalent iodine promoted carbon-halogen bond formation of aryl compounds at ortho-position or para-position of aryl ring.The main content is as follows:1.The progress in hypervalent iodine chemistry in recent years was simply presented.The hypervalent iodine reagents as an easy availability,high efficient and environmentally friendly reagent has been widely applied in organic synthesis.In this section,we have mainly described the research in some aspects of hypervalent iodine chemistry such as oxidation reaction,radical raction,C-C bond formation,C-hetero bond formation and difunctionalization reaction.What's more,we briefly introduced the approaches to form C-X(X=Cl,Br,I)bond through C-H bond activation in recent years,and the recent research progress in synthesis of N-heterocycles including phenanthridine and isoquinoline derivatives have been briefly reviewed as well.2.The two known hypervalent iodines,were synthesized,played a dual role of halogen source and oxidant in selective ortho-chlorination and ortho-bromination of oxime ether using palladium acetate as catalyst.Moreover,reaction with other N-containing directing group was compatible with the reaction conditions,resulting in a good result.In addition,without catalyst,hypervalent iodine enabled para-chlorination and para-bromination.3.Based on previous works,our group synthesized a series of phenanthridine deriatives and isoquinoline deriatives under metal free condition with phenyl isocyanides or vinyl isocyanides as materials and(diacetoxyiodo)benzene as oxidant.Compare to some similar reaction with transition metal as catalyst,the protocol in this thesis,with green condition and short reaction time,is suitable for both phenyl isocyanides and vinyl isocyanides.The thesis proposed some methods using hypervalent iodine reagents to construct aryl carbon-halogen bond,and synthesize N-containg heterocycle.The methods offered scientific theory basis and experimental basis for synthesis and application of aryl halides and N-containg heterocycles.