Ligand-Enabled ortho -Selective C-H Olefination of Tertiary Aniline Derivatives.

A highly ortho -selective C Ar -H olefination of tertiary anilines without a directing group was developed. This reaction tolerated various substituted arenes and olefin coupling partners, affording ortho -olefination products in moderate to good yields. Preliminary mechanistic studies showed that N -Ac-d-Ala, Ag 2 CO 3 , and BQ were the key factors for tuning the regioselectivity from para to ortho . Density functional theory was used to achieve a theoretical understanding of the ortho selectivity.