Construction Of C-C And C-S Bonds Based On Oxidative Decarbonylation Of Aliphatic Aldehyde

Cyano group is an important functional group,which widely exists in bioactive compounds and drug molecules.The introduction of cyano group through the dual function of alkenes is a simple and efficient way.On the other hand,thioether structural units widely exist in natural products with physiological activities and synthetic drugs.Therefore,the development of novel and efficient methods to construct C-S bonds has attracted extensive attention.Therefore,the main content of this paper is to use aliphatic aldehydes as alkylation reagents,through the decarbonylation reaction initiated by free radicals to generate alkyl radicals,and realize the coupling reaction with styrene and TMSCN decarbonylation alkyl-cyanidation,as well as diaryl sulfide derivatives.These two reactions are completed by one pot method with simple conditions,simple operation and good substrate universality.The details are as follows:1.A copper catalyzed decarbonylation alkyl cyanidation of styrene derivatives with aliphatic aldehydes and TMSCN has been developed to provide nitrile compounds with carbon chain extension.Using TBHP as oxidant and free radical initiator,α-di-substituted,α-mono-substituted and linear aliphatic aldehydes were successfully converted into corresponding 3~o,2~oand 1~oalkyl radicals,and then difunctionalized alkyl-cyanidation of alkenes with alkenes and TMSCN.Efficiently construct C(sp~3)-C(sp~3)and C(sp~3)-CN bonds in one step.2.A copper catalyzed decarbonylation of aliphatic aldehydes with diaryl sulfide derivatives has been developed to provide aryl alkyl sulfide with carbon chain extension.Using DTBP as oxidant and free radical initiator,the method can convertα-di-substituted,α-mono-substituted and linear aliphatic aldehydes into corresponding3~o,2~oand 1~oalkyl radicals to form C(sp~3)-S bonds.