Iodide Anion Enables a Reductive Cross‐Electrophile Coupling for Preparing Tertiary Amines

Abstract 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.