Study On Intramolecular Radical Cyclization/Rearrangement Of Vinyl Azide

The unique structure of azide consists of a continuous three nitrogen atoms,which proceeds a wide range of reactions.The vinyl azide as a special class of azide compounds can not only react on azide moiety to achieve many cycloaddition reactions,but also can undergo free-radical cyclization,intramolecular rearrangement and among others.A series of nitrogen-containing organic compounds such as nitrogen heterocycles,amides,and amines can be synthesized,and these structures are key structures of some complex drugs and natural products.Therefore,vinyl azides have been one of the research interests during the development of organic azides more than one hundred years.Vinyl azides have high reactivity and enable to undergo many types of reactions.Based on previous studies,this thesis further studied the radical cyclization and rearrangement reactions of vinyl azides.The main contents of this thesis include the following three chapters:1.Using vinyl azides as substrates,utilization of azide/diacetate iodobenzene system to generate azide free radicals,6-nitrile phenanthridine compounds were successfully synthesized,and further transformation of the resultant 6-nitrile phenanthridines to 6-carboxyphenanthridine and 6-carboxamidephenanthridine have also been investigated.2.With vinyl azide compounds as substrates,tertiary alkylation of terminal olefins has been achieved by using azo compounds(AIBME/AIBN)as the alkylating sources instead of halogenated alkanes.Thus,a variety of phenanthridines containing one quaternary carbon center were synthesized via radical addition/cyclization without external oxidants.3.With vinyl azides as the substrates and potassium persulfate as the radical initiator,Schimidt-type rearrangement of vinyl azides has successfully achieved to afford various functionalized acetanilides without the addition of protic or Lewis acids.This reaction is promoted by the in situ generated protic acid from potassium persulfate and water.