Photoinduced Cleavage of Alkenyl Fluorides for Nucleophilic Acyl Substitution via In Situ Generated Acyl Fluorides

Acyl fluorides are versatile intermediates desired for their stability and unique reactivity with amines and other nucleophiles, enabling targeted nucleophilic acyl substitution reactions. Despite their utility, practical methods for their synthesis remain limited. Herein, we describe a facile, one-pot protocol to generate acyl fluorides from alkenyl fluorides, the first example of acyl fluoride generation from alkenyl moieties. The transformation is promoted by the visible-light photoexcitation of 4-nitrophthalonitrile, which serves as a photooxidant under anaerobic conditions to cleave the alkenyl fluoride, producing the desired acyl fluoride intermediate along with a carbonyl byproduct. We demonstrate the synthetic utility of this mild and practical approach in the synthesis of linear peptide fragments, highlighting its potential application in chemical biology.