Cu-Catalyzed Double C(sp 3 )-H Functionalization of Ethylarenes to Form Arylethanolamines.

A double C(sp 3 )-H functionalization of ethylarenes with alcohols and N -fluorobenzenesulfonimide is reported. The reaction proceeds in three stages. (1) Cu-catalyzed benzylic alkoxylation of ethylarenes gives 1-(1-alkoxyethyl)benzenes. (2) The resulting 1-(1-alkoxyethyl)benzenes are gradually converted into vinylarenes. (3) Cu-catalyzed aminoalkoxylation of the intermediary vinylarenes yields arylethanolamines. Overall, the C-N and C-O bonds are introduced regioselectively at the homobenzylic and benzylic positions of ethylarenes.