Three‐Component Perfluoroalkylvinylation of Alkenes Enabled by Dual DBU/Fe Catalysis**

Herein, a simple and efficient strategy that involves dual 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)/iron-catalyzed alkene perfluoroalkylvinylation by using perfluoroalkyl iodides and 2-aminonaphthalene-1,4-diones as coupling partners is demonstrated. In terms of the developed catalytic system, various styrenes and aliphatic alkenes are well-tolerated, leading to the accurate preparation of perfluoroalkyl-containing 2-aminonaphthalene-1,4-diones in excellent regioselectivity. Moreover, the protocol can be readily applied in late-stage modifications of natural products and pharmaceuticals. The title reactions are featured by easily accessible and inexpensive catalysts and substrates, broad substrate applicability, and mild reaction conditions. Mechanistic investigations reveal a tandem C-I cleavable alkylation and C-C vinylation enabled by cooperative DBU/iron catalysis.