Ambiphilic Reactivity of SF<sub>5</sub>‐Alkynes Applied to Regioselective and Stereodivergent Halogenation Reactions: An Experimental and Theoretical Case Study - Université de Pau et des Pays de l'Adour Accéder directement au contenu
Article Dans Une Revue Advanced Synthesis and Catalysis Année : 2024

Ambiphilic Reactivity of SF5‐Alkynes Applied to Regioselective and Stereodivergent Halogenation Reactions: An Experimental and Theoretical Case Study

Résumé

We explored the ambiphilic reactivity of SF 5 ‐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 SF 5 ‐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 SF 5 ‐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 SF 5 ‐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.
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Dates et versions

hal-04606248 , version 1 (10-06-2024)

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David Matchavariani, Lucas Popek, Jorge Juan Cabrera‐trujillo, Thi Mo Nguyen, Nicolas Blanchard, et al.. Ambiphilic Reactivity of SF5‐Alkynes Applied to Regioselective and Stereodivergent Halogenation Reactions: An Experimental and Theoretical Case Study. Advanced Synthesis and Catalysis, In press, ⟨10.1002/adsc.202400446⟩. ⟨hal-04606248⟩
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