Iridium‐Catalyzed Intermolecular Azide–Alkyne Cycloaddition of Internal Thioalkynes under Mild Conditions

An iridium‐catalyzed azide–alkyne cycloaddition reaction (IrAAC) of electron‐rich internal alkynes is described. It is the first efficient intermolecular AAC of internal thioalkynes. The reaction exhibits remarkable features, such as high efficiency and regioselectivity, mild reaction conditions, easy operation, and excellent compatibility with air and a broad spectrum of organic and aqueous solvents. It complements the well‐known CuAAC and RuAAC click reactions.