Deoxyfluorination of Hydroxy-Substituted Boronates

A practical and scalable protocol for the deoxyfluorination of hydroxyalkyl-substituted aryl- and alkenylboronates was developed. The optimized conditions (combining Deoxo-Fluor with TEA·3HF as the reagents and substrate preconversion to trifluoroborate salts) enabled efficient transformation across a wide range of (homo)benzylic and allylic alcohols while tolerating protected carboxyl and amino groups. The resulting fluorinated boronates performed well as versatile building blocks in oxidation and Suzuki cross-coupling reactions. Furthermore, a telescoped one-pot strategy allowed direct utilization of crude fluorinated intermediates, enabling access to complex molecular frameworks containing alcohol, carbonyl, and ester functionalities, typically intolerant to late-stage fluorination conditions. This methodology offers a general and efficient route for the incorporation of monofluorinated aliphatic fragments into structures that are relevant for medicinal chemistry and materials science.