Access to N−CF(3) Formamides by Reduction of N−CF(3) Carbamoyl Fluorides

The departure into unknown chemical space is essential for the discovery of new properties and function. We herein report the first synthetic access to N‐trifluoromethylated formamides. The method involves the reduction of bench‐stable NCF(3) carbamoyl fluorides and is characterized by operational simplicity and mildness, tolerating a broad range of functional groups as well as stereocenters. The newly made N−CF(3) formamide motif proved to be highly robust and compatible with diverse chemical transformations, underscoring its potential as building block in complex functional molecules.