Access to N−CF3 Formamides by Reduction of N−CF3 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 NCF3 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−CF3 formamide motif proved to be highly robust and compatible with diverse chemical transformations, underscoring its potential as building block in complex functional molecules. The first synthetic access to N‐trifluoromethylated formamides is reported. The method involves the reduction of bench‐stable N−CF3 carbamoyl fluorides. In contrast to e.g. N−Me formamides, the newly made N−CF3 formamides do not show rotamers at room temperature. Moreover, they are highly robust and compatible with diverse chemical transformations.