A Conjugated Microporous Polymer for Palladium‐Free, Visible Light‐Promoted Photocatalytic Stille‐Type Coupling Reactions

The Stille coupling reaction is a versatile method to mainly form aromatic C—C bonds. However, up to now, the use of palladium catalysts is necessary. Here, a palladium‐free and photocatalytic Stille‐type coupling reaction of aryl iodides and aryl stannanes catalyzing a conjugated microporous polymer‐based phototcatalyst under visible light irradiation at room temperature is reported. The novel coupling reaction mechanism occurs between the photogenerated aryl radical under oxidative destannylation of the aryl stannane, and the electron‐activated aryl iodide, resulting into the aromatic C—C bond formation reaction. The visible light‐promoted Stille‐type coupling reaction using the polymer‐based pure organic photocatalyst offers a simple, sustainable, and more economic synthetic pathway toward palladium‐free aromatic C—C bond formation.