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.

Rapid Generation of P(V)-F Bonds Through the Use of Sulfone Iminium Fluoride Reagents.

Phosphorus-fluorine bonds have become increasingly relevant in the pharmaceutical industry. To continue their exploration, more efficient synthetic methods are needed. Here, we report the application of sulfone iminium fluoride (SIF) reagents to the synthesis of P(V)-F bonds. The SIF reagents promote the deoxyfluorination of phosphinic acids in just 60 s with excellent yields and scope. The same P(V)-F products can also be synthesized from secondary phosphine oxides using an SIF reagent.

Synthesis of Highly Reactive Sulfone Iminium Fluorides and Their Use in Deoxyfluorination and Sulfur Fluoride Exchange Chemistry.

We report the synthesis of sulfone iminium fluorides (SIFs), a reactive class of sulfur(VI) molecules. The synthesis is tolerant of a variety of substituents on the sulfur and nitrogen components. The SIF reagents were applied to the deoxyfluorination of alcohols and carboxylic acids, providing high yields of fluorinated products in 60 s at room temperature. The SIF reagents were then utilized in sulfur fluoride exchange (SuFEx), creating the first ionic SuFEx products to date.