An electrochemical γ-C–H arylation of amines in continuous flow

• José A.Forni^a
• Milena L.Czyz^a
• David W.Lupton^b
• Anastasios Polyzos^a,c

• ^aSchool of Chemistry, The University of Melbourne, Parkville 3010, Victoria, Australia
• ^bSchool of Chemistry, Monash University, Clayton 3800, Victoria, Australia
• ^cCSIRO Manufacturing, Research Way, Clayton VIC 3168, Australia

Reported here is a regioselective C(sp₃)–C(sp₂) cross coupling reaction between inert γ-C(sp₃)–H bonds in aliphatic amines and cyanoarenes under electrochemical conditions in flow. The developed methodology takes advantage of a removable redox active auxiliary, which triggers selective 1,7-hydrogen atom transfer to functionalise an aliphatic C–H bond at the γ-position of an alkyl amine. In this reaction, a cyanoarene radical anion functions as both a selective arylating reagent and a redox active mediator, enabling the controlled one electron reduction of the redox active auxiliary. This strategy offers a new approach towards γ-C(sp₃)–H bond functionalisation allowing generation of, amongst others, sterically crowded carbon centres under mild reaction conditions and in the absence of additional catalysts or radical initiators.

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