Iodine Promoted Difunctionalization Of Alkenes

As a kind of simple and important molecules,alkenes are broadly applied in the pharmaceutical chemistry and chemical industry.On the other hand,they are also important starting materials for organic synthesis.A series of skeletons with different functional groups can be obtained quickly by addition of alkenes.With the efforts of organic chemists,many methods have been developed to build new C-N bond or C-S bond from alkenes.Recently developments in amination and sulfenylation of alkenes.were introduced in the first chapter of this dissertation.However,most of these methods are catalyzed by transition metals,even promoted by equivalent metal compounds.This results in metal residues in the products,limiting the application of these methods in the synthesis of drug and other bioactive molecules.We think that this problem can be solved by metal-free catalyzation.In this dissertation,we developed iodine-catalyzed(or promoted)sulfenylation and amination of alkenes to afford a series of heterocycles.The research achievements can be described as three parts as below:1.Synthesis of indolones by iodine-promoted aryl sulfenylation of alkenesThioindolone derivatives were synthesized from N-arylacrylamide by iodine promoted aryl sulfenylation.The reaction conditions were mild and the only by-product was iodized salt.Compared with other sulfenylation reagents,disulfide is more convenient to be stored and used because it is not sensitive to water or oxygen.2.Synthesis of benzoxazines by iodine-promoted oxy-sulfenylation of alkenesSulfonated benzoxazines were successfully synthesized through the oxy-sulfenylation of alkenes.Disulfide and N-(2-(1-phenylvinyl)phenyl)benzamide were used as the starting materials and iodine as the oxidant in this method.The reaction condition is mild and the compatibility is great.3.Synthesis of indolines by iodine-catalyzed amino-functionalization of alkenes in waterWe developed the first amino-functionalization of alkenes in water.Catalyzed by quaternary ammonium salt of iodine,various nucleophiles(such as carboxylic acid,amine,sodium azide,etc.)were reacted with o-aminostyrene to obtain different substituted indolines.It should be noted that H2O2 can be used as oxidant in this reaction,so that the only by-product of this transformation is water.