Ligand-Determined Single, Double, and Triple C–H Arylation of Aryl Phosphines at Will

Yu, Zhiqian; Liu, Qianhui; Yang, Yudong; You, Jingsong

doi:10.1021/acscatal.2c03994

Cited by 14 publications

(2 citation statements)

References 45 publications

(14 reference statements)

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“…After we filed our work report, the You research group reported similar work on the phosphine-directed rhodium-catalyzed arylation reaction. 35 Differing from our strategy, they achieved control over the number of C−H arylations by adding various types of phenol ligands.…”

Section: C−h Arylation Of Phosphinesmentioning

confidence: 99%

“…It is noteworthy that the integration of bromoferrocene into the phosphine scaffold has been achieved, culminating in the synthesis of a novel compound adorned with three ferrocene units. After we filed our work report, the You research group reported similar work on the phosphine-directed rhodium-catalyzed arylation reaction . Differing from our strategy, they achieved control over the number of C–H arylations by adding various types of phenol ligands.…”

Section: Introductionmentioning

confidence: 99%

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Late-Stage Diversification of Phosphines by C–H Activation: A Robust Strategy for Ligand Design and Preparation

Li,

Shi

2024

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS:The advent of the twenty-first century marked a golden era in the realm of synthetic chemistry, exemplified by groundbreaking advancements in the field of C−H activation, which is a concept that quickly transitioned from mere academic fascination to an essential element within the synthetic chemist's toolkit. This methodological breakthrough has given rise to a wealth of opportunities spanning a wide range of chemical disciplines. It has facilitated the late-stage diversification of elaborate organic frameworks, encompassing the spectrum from simple methane to complex polymers, thus refining the lead optimization process and easing the production of diverse molecular analogues. Among these strides forward, the development of phosphorus(III)-directed C−H activation stands out as an increasingly significant and inventive approach for the design and synthesis of ligands, substantially redefining the contours of synthetic methodology. Phosphines, renowned for their roles as ligands and organocatalysts, have become fundamentally important in modern organic chemistry. Their efficiency as ligands is significantly affected by coordination with transition metals, which is essential for their involvement in catalytic processes, influencing both the catalytic activity and the selectivity. Historically, the fabrication of phosphines predominantly relied on synthesis employing complex, multistep procedures. Addressing this limitation, our research has delved into ligand design and synthesis through innovative catalytic P(III)-directed C−H activation strategies. In this Account, we have explored a spectrum of procedures, including direct arylation using metal catalysis, and ventured further into domains such as C−H alkylation, alkenylation, aminocarbonylation, alkynylation, borylation, and silylation. These advances have enriched the field by providing efficient methods for the late-stage diversification of biaryl-type monophosphines as well as enabled the C−H activation of triphenylphosphine and its derivatives. Moreover, we have successfully constructed libraries of diverse axially chiral binaphthyl phosphine ligands, showcasing their potency in asymmetric catalysis. Through this Account, we aim to illuminate the exciting possibilities presented by P(III)-directed C−H activation in propelling the boundaries of organic synthesis. By highlighting our pioneering work, we hope to inspire further developments in this promising field of chemistry.

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Section: C−h Arylation Of Phosphinesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Late-Stage Diversification of Phosphines by C–H Activation: A Robust Strategy for Ligand Design and Preparation

Li,

Shi

2024

Acc. Chem. Res.

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Remote Selective C−H Halogenation of Arylphosphine Oxides with Ferric Halides

Dang

Jia

et al. 2023

Adv Synth Catal

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We developed the remote selective C–H bromination for the synthesis of C4′‐brominated biarylphosphine oxides using FeBr3 as a brominating reagent. C3′‐Brominated products were obtained in reactions with substrates bearing a 2,4,6‐triisopropyl substituent on the bottom ring. Moreover, direct access to C5‐chlorinated peri‐substituted(1‐naphthalenyl)phosphines is developed using FeCl3 as a chlorinating reagent. These halogenated compounds can be utilized for cross‐coupling reactions to construct functionalized phosphine oxides.

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Ru₃(CO)₁₂‐Catalyzed Modular Assembly of Hemilabile Ligands by C−H Activation of Phosphines with Isocyanates

Lin

Zhang

et al. 2022

Angewandte Chemie

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Hemilabile ligands have been applied extensively in transition metal catalysis, but preparations of these molecules typically require multistep synthesis.Here, modular assembly of diverse phosphine-amide ligands, including related axially chiral compounds, is first reported through ruthenium-catalyzed CÀ H activation of phosphines with isocyanate directed by phosphorus(III) atoms. High reactivity and regioselectivity can be obtained by using a Ru 3 (CO) 12 catalyst with a mono-N-protected amino acid ligand. This transformation significantly expands the pool of phosphine-amide ligands, some of which have shown excellent efficiency for asymmetric catalysis. More broadly, the discovery constitutes a proof of principle for facile construction of hemilabile ligands directly from the parent monodentate phosphines by CÀ H activation with ideal atom, step and redox economy. Several dinuclear ruthenium complexes were characterized by single-crystal X-ray diffraction analysis revealing the key mechanistic features of this transformation.

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Ligand-Determined Single, Double, and Triple C–H Arylation of Aryl Phosphines at Will

Cited by 14 publications

References 45 publications

Late-Stage Diversification of Phosphines by C–H Activation: A Robust Strategy for Ligand Design and Preparation

Late-Stage Diversification of Phosphines by C–H Activation: A Robust Strategy for Ligand Design and Preparation

Remote Selective C−H Halogenation of Arylphosphine Oxides with Ferric Halides

Ru₃(CO)₁₂‐Catalyzed Modular Assembly of Hemilabile Ligands by C−H Activation of Phosphines with Isocyanates

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Ligand-Determined Single, Double, and Triple C–H Arylation of Aryl Phosphines at Will

Cited by 14 publications

References 45 publications

Late-Stage Diversification of Phosphines by C–H Activation: A Robust Strategy for Ligand Design and Preparation

Late-Stage Diversification of Phosphines by C–H Activation: A Robust Strategy for Ligand Design and Preparation

Remote Selective C−H Halogenation of Arylphosphine Oxides with Ferric Halides

Ru3(CO)12‐Catalyzed Modular Assembly of Hemilabile Ligands by C−H Activation of Phosphines with Isocyanates

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Ru₃(CO)₁₂‐Catalyzed Modular Assembly of Hemilabile Ligands by C−H Activation of Phosphines with Isocyanates