A highly α-regioselective In(OTf)3-catalyzed N-nucleophilic substitution of cyclic Baylis–Hillman adducts with aromatic amines

The highly α-regioselective N-nucleophilic substitution of B–H adducts bearing five (1a–f) or six-membered ring (5a–e) moieties with aromatic amines (2a–e) was developed under the catalysis of In(OTf)3 (10 mol%). During the reaction the allylic rearrangement from γ-product to α-product occurred, resulting in thermodynamically stable α-product predominately.