Electrochemical Desilylative Fluorination Enables Access to N ‐Monofluoromethyl Amides and Peptides

N ‐Fluoroalkyl amides have emerged as highly attractive targets because N ‐fluoromethylation can modulate conformation, stability, lipophilicity, and molecular recognition. However, despite the rapidly advancing chemistry of N ‐CF 3 and N ‐CF 2 H amides, access to the corresponding N ‐monofluoromethyl ( N ‐CH 2 F) amides remains significantly underdeveloped. Existing approaches are often constrained by the use of silver‐based fluorinating reagents, unstable intermediates, and limited compatibility with peptide substrates. In this study, we report an electrochemical strategy for the synthesis of N ‐monofluoromethyl amides using fluoride as the fluorine source. Employing N ‐CH 2 TMS amides as readily accessible precursors, the target framework is efficiently constructed through electrochemical oxidative activation. The transformation proceeds under mild conditions and exhibits broad compatibility with amino acid‐derived amides and peptide substrates of varying chain lengths.