Advances in dicarbofunctionalization of alkenes, alkynes and allenes via iron catalysis

Transition metal-catalyzed dicarbofunctionalization of unsaturated bonds, which enables the simultaneous installation of two carbon substituents at vicinal positions, offers an efficient strategy for constructing complex molecular architectures. This approach is particularly valuable in the synthesis of natural products and pharmaceuticals, where rapid diversification of carbon frameworks is essential. While transition metals such as palladium have traditionally dominated this area, concerns over their limited availability and high cost have driven the development of more sustainable catalytic systems. In recent years, iron-catalyzed dicarbofunctionalization of unsaturated bonds has emerged as a powerful alternative for the formation of diverse C-C bonds. This review provides a systematic overview of iron-catalyzed three-component dicarbofunctionalization of alkenes, alkynes, and allenes employing organomagnesium, organozinc and organolithium reagents as the coupling partners. Particular emphasis is placed on the practical applications of these methods, along with detailed discussions of reaction mechanisms and selectivity control. Finally, current limitations are discussed, and future directions are proposed, including strategies for achieving stereocontrol and enabling reductive couplings between two electrophilic partners.