Three-Component Coupling Involving Arynes, Aromatic Tertiary Amines, and Aldehydes via Aryl–Aryl Amino Group Migration

The transition-metal-free multicomponent coupling of arynes, aromatic tertiary amines, and aldehydes proceeding via the aryl to aryl amino group migration has been demonstrated. This protocol allows rapid access to <i>ortho</i>-functionalized tertiary amines in moderate to good yields. Moreover, activated ketones can also be used as the aldehyde component in the present reaction. The similarity of the aryl–aryl tertiary amino group migration with the Smiles rearrangement is striking