Research On Oxidative Functionalization Of Alkenes Throug Radical Process

The direct functionalization of alkenes are not only a powerful strategy for the synthesis of various organic compounds,but also a simple,efficient,and versatile routes for the formation of carbon-carbon,carbon-nitrogen and carbon-oxygen bonds.Recently,the radical triggered oxidative functionalization of alkenes is a hot topic in organic synthesis and a few excellent methodologies have been reported,which will largely extension the application of alkenes in organic chemistry.In this thesis,we focuse our attention on the radical triggered addition/?-elimilation?addition/substitution?addition/hydrolysis and 1,2-difunctionalization of alkenes,which will develop some novel methods to construct various functionalized alkenes and new C-X bond formation.This dissertation is made up of six chapters:Chapter 1:In this part,the radical triggered oxidative functionalization of alkenes with various functionalization groups is summarized.The contents are classified by different C-X bond formation.Chapter 2:In this part,we have developed a tetrabutylammonium iodide catalyzed method for the synthesis of allyl aryl sulfones using Baylis-Hillman acetates and sulfonylhydrazides as starting materials and tert-butyl hydroperoxide as oxidation in water.This method afford diverse substituted allyl aryl sulfones in moderate to good yields.Chapter 3:In this part,we focused our attention on the synthesis of alkoxycarbonylated oxindoles and isoquinolinedione derivatives through radical pathway.The reported reactions employ easily accessible and safe carbazates as alkoxycarbonyl radical precursors.These methods provide a simple,safe,and environmentally friendly CO-free strategies for alkoxycarbonylation reactions.Chapter 4:In this part,we have developed a radical triggered oxidative functionalization of enamides.By utilizing this strategy,we have achievedthe synthesis of?-keto-sulfones and?-oxo-ketones.Chapter 5:In this part,we have developed a practical method to afford functionalized ketones by employing enol acetates as starting materials.By utilizing this strategy,we developed a complementary method to afford?-keto-sulfones,which avoid the shortages of our previous work in chapter 4.Meanwhile,we have achieved a tert-butyl hydrogenperoxide(TBHP)mediated radical alkylation of enol acetates with alcohols,which provide a new route to?-hydroxy-ketons.Compared to Aldol reaction,this method is metal-free,acid and base free.Notably,some of the synthesized compounds are not easily available by simple aldol reaction.Chapter 6:In this part,we have developed an ₂/TBHP mediated 1,2-difunctionalization of alkenes,thus providing efficient and general access to a variety of?-iodo-N-alkoxyphthalimides.