Palladium-Catalyzed ortho C-H Allylation of Tertiary Anilines

Allyl groups could be transformed into various functional groups. A novel and highly regioselective approach for the Pd-catalyzed ortho C-H allylation of tertiary anilines has been developed. Various tertiary anilines and substitution groups were well-tolerated, and allylated linezolid, ibuprofen, naproxen, ketoprofen, and dehydroabietic acid derivatives were easily prepared. Notably, this new method overcomes the limitations of classical amide-directing groups, as the amide groups are well-tolerated in the reaction. Preliminary mechanistic studies revealed that a dual-ligand effect may be involved in achieving excellent ortho selectivity in this reaction facilitated by N-Bz-Gly and Ag₂CO₃. Further studies indicate that FeCl₃ is necessary as a Lewis acid to activate allyl bromide.