Electrochemical Induced Difunctionalization Of Alkenes And Isocyanides

Organic synthesis plays an extremely important role in the development of human society through the construction of target molecules,which has been widely used from pharmaceutical to materials science.With the development of green and sustainable development,research scholars are committed to developing green,concise and efficient methods to construct target molecules.The development of free radical chemistry has further expanded the field of organic synthesis and provided new ideas for the construction of target compounds.As a kind of green and clean energy,electrochemistry has shown its unique advantages in organic chemical redox,attracting a large number of researchers to devote themselves to the research of organic mechanochemistry.Organic electrosynthesis can avoid unnecessary chemical redox agents.Compared with thermochemistry and photochemistry,electrochemistry shows high efficiency,which is more in line with the requirements of green chemistry and sustainable development strategy.Therefore,electrochemistry provides an effective method for the development of free radical chemistry.The research contents of this paper are as follows:electrochemical induced bifunctionalization of olefins and isonitriles with the participation of free radicals,and the construction of new C-C,C-O,C-Se and C-S bonds.An electrochemical oxidative difunctionalization of allyl alcohols for synthesis ofβ-trifluoromethyl ketones is achieved through 1,2-migration process.A series ofβ-trifluoromethyl ketones can be facilely obtained utilizing CF₃SO₂Na as radical source,eliminating the use of metals and sacrificial chemical oxidants.Importantly,this protocol not only realizes aryl-migration but also offers alkyl-migration products,which provides a good method for the diversity of novel compounds.The results show that the mechanism of the reaction can be related to the migration of carbocations rather than free radicals.The tandem cyclization of olefinic carbonyls with easily accessible diselenides facilitated by electrochemical oxidation has been successfully developed,which provides an environmentally friendly manner for the construction of C-Se and C-O bonds simultaneously.Gram scale experiments and derivatization of the product indicate the potential application value of the reaction.Neither metal catalysts nor external chemical oxidants is required to promote this transformation.A series of novel iminothioethers were constructed by the bifunctional reaction of isonitrile.In this method,thiophenol/mercaptan was used as free radical source and alcohol as nucleophilic reagent,and the electrochemical induced bifunctionalization of isonitrile was successfully realized.This method not only solves the difunctionalization between isonitrile molecules which is difficult to realize,but also produces strong nucleophilic reagent by means of cathodic reduction,that is,oxygen negative nucleophilic reagent,which overcomes the traditional solvent amount of alcohol as nucleophilic reagent or sodium alcohol as nucleophilic reagent.