Article Dans Une Revue ACS Catalysis Année : 2025

Room-Temperature Rh(I)-Catalyzed P(III)-Directed C–H Bond Alkylation: Enhanced Reactivity through Ligand Acceleration

Résumé

Despite the potential of Rh(I)-catalyzed trivalent phosphorus-directed C–H functionalizations to diversify phosphorus-containing molecules, the requirement for harsh reaction conditions has limited its broader application. In this study, we introduce a ligand-accelerated catalysis approach that enables room-temperature C–H bond alkylation of biarylphosphines using a Rh(I) catalyst. Through kinetic investigation, we identified tris(4-trifluoromethylphenyl)phosphine as a privileged ligand that significantly enhances overall processes including catalyst stability and regeneration. Our NMR mechanistic studies revealed the formation of a Rh–H intermediate, providing direct evidence for an oxidative addition pathway. This work expands the utility of Rh(I)-catalyzed C–H functionalization under mild conditions and lays the groundwork for further development of ligand-accelerated strategies in other challenging catalytic processes, particularly those involving strong σ-donor directing groups, holding significant potential to broaden the chemical space of phosphorus-based compounds, with diverse applications.

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hal-04926339 , version 1 (03-02-2025)

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Jian Zhang, Jean-François Soulé. Room-Temperature Rh(I)-Catalyzed P(III)-Directed C–H Bond Alkylation: Enhanced Reactivity through Ligand Acceleration. ACS Catalysis, 2025, 15, pp.2839-2846. ⟨10.1021/acscatal.4c05673⟩. ⟨hal-04926339⟩
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