Transition‐Metal‐Free Approach for Z‐Vinyl Fluorides by Hydrofluorination of Alkynes bearing SF4 and SF5 Groups

Abstract The synthesis of vinyl fluorides plays a crucial role in various scientific disciplines, including pharmaceutical and materials sciences. Herein, we present a direct and stereoselective hydrofluorination method for the synthesis of Z isomers of vinyl fluorides from alkynes containing unexplored SF 5 and SF 4 groups. Our strategy employed tetrabutylammonium fluoride (TBAF) as a fluorine source. It demonstrates high compatibility with aryls, biaryls, heteroaryls, and tert‐alkyl groups, allowing facile incorporation of SF 5 and SF 4 groups across the triple bond without any transition‐metal catalysts. This approach avoids the potential decomposition of the SF 5 or SF 4 units via coordination with transition metals or acidic protic sources. Remarkably, this transformation proceeded at room temperature without any additional additives, providing the Z isomer of vinyl fluorides in excellent yield and high selectivity. The presence of a water molecule as a hydrate in TBAF is essential for efficient conversion. This methodology opens new avenues for the synthesis of enchanting SF 5 ‐ and SF 4 ‐containing fluorinated vinylic scaffolds, thereby providing advanced opportunities for novel drug discovery and fluorinated polymers.