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            <title xml:lang="en">Room-Temperature Rh(I)-Catalyzed P(III)-Directed C–H Bond Alkylation: Enhanced Reactivity through Ligand Acceleration</title>
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            <idno type="halRefHtml">&lt;i&gt;ACS Catalysis&lt;/i&gt;, 2025, 15, pp.2839-2846. &lt;a target="_blank" href="https://dx.doi.org/10.1021/acscatal.4c05673"&gt;&amp;#x27E8;10.1021/acscatal.4c05673&amp;#x27E9;&lt;/a&gt;</idno>
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                <title xml:lang="en">Room-Temperature Rh(I)-Catalyzed P(III)-Directed C–H Bond Alkylation: Enhanced Reactivity through Ligand Acceleration</title>
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              <p>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.</p>
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