Cu-Catalyzed Selective Oxy-Cyanolkylation Of Allylamines With Cycloketone Oxime And Carbon Dioxide

With the increase of carbon dioxide concentration,the increasing influence of greenhouse effect on global climate,but carbon dioxide is also an important part of the carbon cycle of the earth.From a chemical point of view,carbon dioxide,as an ideal carbon-one resource.It is of great academic significance and broad industrial application prospect to the research on conversion of CO₂ as reaction block to construct a series of high value-added chemicals quickly and efficiently.In addition,C-C bond widely exists in kinds of organic chemicals,the direct selective activation and functionalization of C-C bonds recombining the molecular framework and synthesizing unique copies of molecules by a completely different strategy from traditional synthesis methods.However,transition-metal catalyzed C–C bond activation is kinetic challenging due to the coordination of transition metal center with C-C bond and the limitation of orbital direction At the same time,the bond dissociation energy of the C-C bond reaches 90 kcal/mol,which is thermodynamically unfavorable.Transition-metal catalyzed cycloketone oxime esters generates free radicals and then C-C bond Cleavage of strained ring systems and participates in the subsequent reaction,providing a new strategy for the construction of cyano-containing compounds.In conclusion,we have developed a novel Cu-catalyzed selective oxy-cyanoalkylation of allylamines with cycloketone oxime esters and CO₂ via C-C bond cleavage.Valuable cyanoalkyl-substituted 2-oxazolidinones are obtained in good yields with high regio-and chemo-selectivities.This method features mild and redox-neutral conditions,broad substrate scope,good functional group tolerance and easy scalability.The preliminary mechanistic studies indicate that cyanoalkyl radical might be involved in this reaction.Based on these studies,we developed a copper catalyzed selective oxy-cyanoalkylation of allylamines under mild conditions,which is expected to be applied to the fast and efficient construction of oxazolinone.