Scandium-Catalyzed Benzylic C(sp3)–H Alkenylation of Tertiary Anilines with Alkynes

This work describes the chemo- and stereoselective benzylic C­(sp3)–H alkenylation of tertiary ortho-methyl anilines with internal alkynes using a simple β-diketiminato scandium catalyst. This protocol offers an efficient method for the synthesis of a new family of tertiary ortho-allylanilines in high yields. The resultant alkenylation products facilely underwent further chemical transformation to other valuable anilines. A cationic scandium benzyl species was isolated from a stoichiometric reaction and confirmed to be the catalytic intermediate.