Expanded Access to Fluoroformamidines via a Modular Synthetic Pathway.

Fluoroformamidines are an underutilized and understudied functional group despite combining two of the most highly prized elements in drug design: nitrogen and fluorine. We report a practical and modular synthesis of fluoroformamidines via the rearrangement of in situ-generated amidoximes. High yields in just 60 s at room temperature highlight the efficiency of this protocol. Furthermore, fluoroformamidines proved to be useful intermediates in the synthesis of diverse ureas and carbamimidates.

A modified Beckmann rearrangement for the facile synthesis of amidines and imidates via imidoyl fluoride intermediates.

Herein, we report a modified Beckmann rearrangement using sulfone iminium fluoride (SIF) reagents to rapidly synthesize imidoyl fluoride intermediates. Subsequently, amidine and imidate products can be formed following the introduction of amine and alcohol nucleophiles, respectively. Overall, approximately 50 amidine and imidate products have been isolated in high yields utilizing mild conditions.