Affiliation:
1. Université de Haute-Alsace Université de Strasbourg, CNRS LIMA UMR 7042 68000 Mulhouse France
2. CNRS/Université de Pau et des Pays de l'Adour E2S-UPPA IPREM UMR 5254 64053 Pau cedex 09 France
3. CNRS UMR 6014 COBRA Normandie Université 76821 Mont Saint Aignan France
Abstract
AbstractWe explored the ambiphilic reactivity of SF5‐alkynes, and we proved they can act as both nucleophiles and electrophiles. We selected halogenation reactions as benchmark reactions and developed highly selective stereodivergent hydrohalogenation (I, Br, Cl, F) reactions of SF5‐alkynes. The stereochemistry is finely controlled thanks to the nature of the acids used (strong or soft) in the presence of halide source, while the high regioselectivity is governed by the strong polarization of SF5‐alkynes. Mechanistic studies supported by DFT calculations shed light on two different reaction mechanisms responsible of the excellent stereocontrol. This stereoselectivity was quantitatively rationalized with the ASM and EDA methods. A few dihalogenation reactions are reported and DFT calculations rationalize this cis‐stereoselectivity. Relative configuration of all the SF5‐haloalkenes was unambiguously determined by X‐ray diffraction. Noteworthy, several post‐functionalization reactions such as cross‐couplings, cyanation and reductions are described to strengthen the synthetic potential.