Solvent‐Free Ruthenium‐Catalyzed Direct Coupling of Phosphines and Aryl Chlorides via C−H Activation: An Efficient and Straight Access to Aryl‐Substituted Biarylphosphines

Zhang, Ni-Juan; Ma, Wenzhong; Li, Jiawei; Liu, Yuejin; Zeng, Ming‐Hua

doi:10.1002/ajoc.202100161

Cited by 9 publications

(2 citation statements)

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“…The tactic of accomplishing direct arylation via C–H activation has come to the forefront as an exceedingly efficient approach for the synthesis of biaryl compounds, showcasing remarkable atom and step economy . Direct arylation of phosphines is instrumental in establishing a diverse array of C–C bonds, thereby enriching the molecular variety of such ligands. − We embarked on our exploration of this field in 2017, initially focusing on the C–H arylation of phosphines. In that pivotal year, we introduced a cutting-edge technique for tailoring biaryl-type monophosphines through rhodium-catalyzed C–H arylation (Figure ).…”

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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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“…Since the pioneer observation by Hartwig and co-workers on Pd-catalyzed direct polyarylation of 1-(di- tert -butylphosphino)ferrocene, P(III)-chelation-assisted C–H bond functionalization has become a straightforward strategy to quickly generate vast libraries of functionalized phosphines, allowing one to discover an upgraded ligand exhibiting higher catalytic activity than that using Pd catalysis . To date, C–H bond functionalizations of phosphines are limited to arylphosphines (borylation, silylation, and arylation), biarylphosphines (borylation, silylation, arylation, alkylation, alkenylation, and carbonylation), and 1-naphtyphosphines (arylation and alkylation) (Figure ). Interestingly, in some cases, the C–H bond functionalizations of phosphines give birth to a better ligand in transition-metal catalyzed reactions .…”

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Upgrading Carbazolyl-Derived Phosphine Ligands Using Rh^I-Catalyzed P^III-Directed C–H Bond Alkylation for Catalytic CO₂-Fixation Reactions

et al. 2022

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We report an Rh(I)-catalyzed C–H bond alkylation of PhenCarPhos [N-(2-(diphenylphosphaneyl)phenyl)carbazole] and some congener phosphine ligands with alkenes. The C–H bond functionalization occurred exclusively at the C1 position of the carbazolyl unit because the trivalent phosphine acts as a directing group. This protocol provides straightforward access to a large library of C1-alkyl substituted PhenCarPhos, which outperformed common commercial or unfunctionalized phosphines and their precursors in the Pd-catalyzed carbon dioxide-fixation reactions with propargylic amines.

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Ruthenium‐Catalyzedortho‐CH Bond Arylation Reactions

Bruneau¹,

Gramage‐Doria²

2022

Handbook of CH-Functionalization

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The highly selective ruthenium-catalyzed ortho-C-H bond arylations have met a level of maturity that makes them an attractive tool to achieve unique organic transformations.By means of the manifold mechanisms operating in the presence of different arylating agents and reaction conditions, these methodologies have succeeded in reducing the wastes/steps towards the desired molecules as well as enlarging the chemical space by affording molecules impossible to obtain otherwise. The key achievements in this area are discussed in this chapter. Introduction.Biaryl and terphenyl cores are widespread structures in many biologically active substances and have useful physical properties in material sciences. The seminal results on the synthesis of biphenyl by connecting two aryl iodide molecules via reductive coupling in the presence of copper were reported in 1901 [1] and this concept was further developed [2,3]. Since this discovery, continuous efforts have been devoted to the improvement of these aryl-aryl couplings, mainly based on palladium-catalyzed cross-coupling reactions of aryl (pseudo)halides with organometallic reagents leading to the formation of a new C(sp 2 )-C(sp 2 ) bonds (Figure 1a) [4][5][6][7][8].

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Solvent‐Free Ruthenium‐Catalyzed Direct Coupling of Phosphines and Aryl Chlorides via C−H Activation: An Efficient and Straight Access to Aryl‐Substituted Biarylphosphines

Cited by 9 publications

References 51 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

Upgrading Carbazolyl-Derived Phosphine Ligands Using Rh^I-Catalyzed P^III-Directed C–H Bond Alkylation for Catalytic CO₂-Fixation Reactions

Ruthenium‐Catalyzedortho‐CH Bond Arylation Reactions

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Solvent‐Free Ruthenium‐Catalyzed Direct Coupling of Phosphines and Aryl Chlorides via C−H Activation: An Efficient and Straight Access to Aryl‐Substituted Biarylphosphines

Cited by 9 publications

References 51 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

Upgrading Carbazolyl-Derived Phosphine Ligands Using RhI-Catalyzed PIII-Directed C–H Bond Alkylation for Catalytic CO2-Fixation Reactions

Ruthenium‐Catalyzedortho‐CH Bond Arylation Reactions

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Upgrading Carbazolyl-Derived Phosphine Ligands Using Rh^I-Catalyzed P^III-Directed C–H Bond Alkylation for Catalytic CO₂-Fixation Reactions