Copper-catalyzed Cyanoalkylation Of Olefins And Its Application In Peptide Systhesis

Cyano compounds can be widely found in nature,especially in the biological world.Cyanide can be made from certain bacteria,fungi or algae which is found in quite a few foods and plants.In plants,cyanide is usually associated with sugar molecules which is present in the form of cyanogenic glycoside,for example cassava containing cyanogenic glycosides.Cyanide is a very useful reagent in drug synthesis.It is often used to introduce a cyano group into a molecule to form an organic cyanide.Cyano can produce carboxylic acids by hydrolysis and form amines by reduction,even more functional groups can be derived by other reactions.The introduction of an alkyl group on an organic molecule such as carbon,nitrogen,oxygen or the like,and the process of synthesizing an organic compound is referred to as alkylation.Through alkylation,new covalent bonds such as carbon-carbon and carbon-heteroatom bond,etc can be formed,which prolongs the molecular skeleton of organic compoundsand modifying the alkylation structure can change the physical and chemical properties of the original compound,thereby producing many organic chemicals that have specific uses,especially biopharmaceutical active molecules.Dicarbofunctionalizationof alkenes provide a highly efficient way to functionalize alkenes.In this type of reactions,the strategies for arylations and fluoroalkylations have been well developed in the past few years.However,the methods for introduction of alkyl groups were still limited.Alkyl bromide is a commonindustrial feed stocks.It is the direct using of unactivated alkyl bromides in alkylation reaction that will greatly reduce the cost of such chemical conversion.We here report the first example of photoinduced Cu-catalyzed cyanoalkylation of alkenes by direct using alkyl bromides as alkylation reagents.Research shows that this method has good functional group compatibility and 1~o,2~o,and 3~o unactivatedalkyl bromides with various sensitive functional groups were well tolerated with good yields.Notably,the terminal and internal alkenes as well as the alkene-contained peptide were all proceeded well.