Dilithium Amides as a Modular Bis-Anionic Ligand Platform for Iron-Catalyzed Cross-Coupling

Dilithium amides have been developed as a bespoke and general ligand for iron-catalyzed Kumada–Tamao–Corriu cross-coupling reactions, their design taking inspiration from previous mechanistic and structural studies. They allow for the cross-coupling of alkyl Grignard reagents with sp2-hybridized electrophiles as well as aryl Grignard reagents with sp3-hybridized electrophiles. This represents a rare example of a single iron-catalyzed system effective across diverse coupling reactions without significant modification of the catalytic protocol, as well as remaining operationally simple.