Acid-Catalyzed ortho-Alkylation of Anilines with Styrenes:  An Improved Route to Chiral Anilines with Bulky Substituents

Reaction of para-substituted anilines with styrene derivatives at elevated temperatures, when catalyzed by CF3SO3H, results in highly chemoselective ortho-alkylation of the aniline. When R = H, dialkylation can be achieved by varying the ratio of styrene to aniline. Several different substituted anilines and styrenes were examined, and good yields (42−87%) were obtained, except in the case where electron-withdrawing substituents are present on the styrene.