Synthesis and Reactivity of s -Aryltetrazines Palladacycles Toward a Direct o -Aryl C–H Bond Halogenation Achieved by Electrocatalysis - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Organometallics Année : 2024

Synthesis and Reactivity of s -Aryltetrazines Palladacycles Toward a Direct o -Aryl C–H Bond Halogenation Achieved by Electrocatalysis

Asmae Bousfiha
  • Fonction : Auteur
Sophie Fournier
  • Fonction : Auteur
Hélène Cattey
  • Fonction : Auteur
Paul Fleurat-Lessard
Charles Devillers
Dominique Lucas
  • Fonction : Auteur
Julien Roger

Résumé

ABSTRACT: Electrocatalysis is considered a promising approach towards cleaner, precisely controlled, and low waste-producing transition metal-catalyzed C–H bond activation/functionalization. However, some useful redox active substrates could be challenging to use in electrocatalysis, depending on their redox potential and intrinsic reactivity. Accordingly, the topical s-aryltetrazines have not been employed, up to now, for their selective transition metal-promoted ortho-C–H functionalization using an electrocatalytic process. Herein, we addressed this challenging issue stepwisely by synthesizing first a series of stable and well-defined dinuclear and mononuclear palladacycles of the s-diphenyltetrazine. These compounds are considered as pertinent intermediates of direct C–H functionalization of s-aryltetrazines in a palladium-catalyzed approach. The palladium complexes were characterized by multinuclear NMR spectroscopy in solution, and single crystal X-ray diffraction analysis in the solid state. Their electrochemical behavior was established by cyclic voltammetry. We successfully achieved the reductive elimination of o-C–H halogenated s-diphenyltetrazine under electrochemical conditions from its corresponding mononuclear o-metallated s-aryltetrazine palladium halide, establishing the electrochemically controlled palladium-promoted o-C–H halogenation of a s-aryltetrazine. From this elementary step achieved under electrocatalytic control, we devised simple conditions for effective electrochemical palladium-catalyzed C–H ortho-chlorination and iodination of s-aryltetrazines, using cheap lithium halide salt as nucleophile source. While these conditions still suffer from multiple halogenation reactions, and especially the symmetrical bis-halogenation, they open the way, as proof-of-concept, to unprecedented electrochemically controlled direct functionalization of the redox active s-aryltetrazines.

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Chimie
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hal-04535744 , version 1 (07-04-2024)

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Asmae Bousfiha, Sophie Fournier, Hélène Cattey, Paul Fleurat-Lessard, Charles Devillers, et al.. Synthesis and Reactivity of s -Aryltetrazines Palladacycles Toward a Direct o -Aryl C–H Bond Halogenation Achieved by Electrocatalysis. Organometallics, 2024, ⟨10.1021/acs.organomet.3c00497⟩. ⟨hal-04535744⟩
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