Iodide anion enables a reductive cross-electrophile coupling for preparing tertiary amines.

The reducing power of iodide anion is an underexplored property that can be used for the cross-electrophile coupling of organic molecules. Herein we harness this trait for the preparation of tertiary amines through the combination of two simple reagents: an electrophilic-carbon precursor and an iminium iodide in a dual role-both as nitrogen-containing building block and as reducing agent. The underlying mechanism of this new C-C bond-formation paradigm is explored through a combination of experiment and quantum chemical calculations.