Ruthenium–NHC complex-catalyzed P(<scp>iii</scp>)-directed C–H borylation of arylphosphines

Thongpaen, Jompol; Manguin, Romane; Kittikool, Tanakorn; Camy, Aurèle; Roisnel, Thierry; Dorcet, Vincent; Yotphan, Sirilata; Canac, Yves; Mauduit, Marc; Baslé, Olivier

doi:10.1039/d2cc03909e

Cited by 8 publications

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“…Moreover, they also exhibit properties as a significant class of frustrated Lewis pairs (FLPs), which have been extensively investigated in numerous captivating stoichiometric and catalytic systems for small-molecule activation and reaction . Over the past decade, substantial advancements have been achieved in the realm of C–H borylation reactions in which P(III)-directing groups have been explored to access boronated phosphines. ,− In this context, our research group uncovered a rhodium-catalyzed, P(III)-chelation-assisted ortho -C–H activation of arylphosphines, utilizing catechol as a ligand (Figure ). To facilitate isolation and purification, further treatment of the mixture with BH 3 ·THF provided borane complexes.…”

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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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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: 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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“…9 Previous reports have evidenced that these bidentate LX type ligands could strongly bind transition metals such as iridium( iii ), 10 rhodium( i / iii ) 11 and ruthenium( ii ) 12 to form robust cyclometallated complexes that notably demonstrated efficient catalytic activities in C–H borylation under thermic and photocatalytic conditions. 11,12 In a continued effort to design novel NHC-based transition-metal catalysts for C–H bond functionalization reactions, we investigated the synthesis of well-defined iridium( i ) complexes combining an electron rich bidentate NHC-carboxylate ancillary ligand and the labile 1,5-cyclooctadiene (cod) ligand. To this end, a series of amino acid-based NHC ligand precursors 1 were converted to their corresponding silver-intermediates and subsequently transmetalated to [Ir(cod)Cl] 2 to afford the desired (NHC)Ir(cod) complexes in good yields (Fig.…”

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“…S6–S9, ESI†). 12,19,20 Moreover, we also compared the rates for the functionalization of 3a using H-SiMePh 2 or D-SiMePh 2 as silylating agent, and a k H / k D value of 2.0 was observed in this case (Fig. 3 and Fig.…”

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confidence: 99%

“…Precursors of unsymmetrical bidentate NHC-carboxylate are accessible through a straightforward multicomponent synthesis which we recently developed. 9 Previous reports have evidenced that these bidentate LX type ligands could strongly bind transition metals such as iridium( iii ), 10 rhodium( i / iii ) 11 and ruthenium( ii ) 12 to form robust cyclometallated complexes that notably demonstrated efficient catalytic activities in C–H borylation under thermic and photocatalytic conditions. 11,12 In a continued effort to design novel NHC-based transition-metal catalysts for C–H bond functionalization reactions, we investigated the synthesis of well-defined iridium( i ) complexes combining an electron rich bidentate NHC-carboxylate ancillary ligand and the labile 1,5-cyclooctadiene (cod) ligand.…”

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Iridium(i) complexes with bidentate NHC ligands as catalysts for dehydrogenative directed C–H silylation

et al. 2023

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Merging Visible Light Photocatalysis and P(III)‐Directed C−H Activation by a Single Catalyst: Modular Assembly of P‐Alkyne Hybrid Ligands

Jiang,

Yang,

Lin

et al. 2023

Angewandte Chemie

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Metal‐catalyzed C−H activation strategies provide an efficient approach for synthesis by minimizing atom, step, and redox economy. Developing milder, greener, and more effective protocols for these strategies is always highly desirable to the scientific community. In this study, the utilization of a single rhodium complex enabled the visible‐light‐induced late‐stage C−H activation of biaryl‐type phosphines with alkynyl bromides, employing inherent phosphorus atoms as directing groups. This chemistry combines P(III)‐directed C−H activation with visible light photocatalysis, under exogenous photosensitizer‐free conditions, offering a unique platform for ligand design and preparation. Furthermore, this study also explores the asymmetric catalysis and coordination chemistry of the resulting P‐alkyne hybrid ligands with specific transition metals. Experimental results and density functional theory calculations demonstrate the mechanistic intricacies of this transformation.

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Ruthenium–NHC complex-catalyzed P(iii)-directed C–H borylation of arylphosphines

Abstract: NHC)(arene)Ru(II) complexes with bidentate LX-type NHC-carboxylate ligands were efficiently synthesized and fully characterized including solid-state structures. The strong coordination of the NHC carboxylate ligand and the labile character of the...

Cited by 8 publications

References 48 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

Iridium(i) complexes with bidentate NHC ligands as catalysts for dehydrogenative directed C–H silylation

Merging Visible Light Photocatalysis and P(III)‐Directed C−H Activation by a Single Catalyst: Modular Assembly of P‐Alkyne Hybrid Ligands

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