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 ortho-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.本研究证实了无需过渡金属参与的芳炔（arynes）、芳香族叔胺与醛类的多组分偶联反应，该反应经由芳基向芳基氨基迁移的路径进行。该合成策略可快速制备邻位官能化叔胺，产物收率可达中等至优异水平。此外，活化酮类亦可作为醛类组分应用于本反应体系中。值得注意的是，该芳基-芳基叔氨基迁移过程与斯迈尔斯重排（Smiles rearrangement）具有极为显著的相似性。