Ferrocenyl (P,N)-diphosphines incorporating pyrrolyl, imidazolyl or benzazaphospholyl moieties: Synthesis, coordination to group 10 metals and performances in palladium-catalyzed arylation reactions

Allouch, Fatima; Vologdin, Nikolay; Cattey, Hélène; Pirio, Nadine; Naoufal, Daoud; Kanj, Ali; Smaliy, Radomyr V.; Savateev, Aleksandr; Marchenko, A. P.; Hurieva, Anastasia N.; Koidan, Heorgii; Kostyuk, Alexander; Hierso, Jean‐Cyrille

doi:10.1016/j.jorganchem.2013.03.025

Cited by 17 publications

(7 citation statements)

References 27 publications

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“…Tris( N -pyrrolyl)phosphine , is a weak electron donor and good π-acceptor ligand, which has been successfully applied in hydroformylation reactions. − The C2-connected structural isomer, tris(1-methylpyrrol-2-yl)phosphine, was first reported in 1974, followed by several derivatives of (1-methylpyrrol-2-yl)phosphines. − Yet, the properties of these phosphines have barely been investigated. , Among them, the cataCXium ligands represent a prominent class of N -arylated pyrrolylphosphines, which have been used in Suzuki cross-coupling reactions . Few reports exist about C3-bound pyrrolylphosphines. ,,− In fact, the only representative with three pyrrolyl groups, tris(1- tert -butylpyrrol-3-yl)phosphine, has been generated in situ but was not isolated, and the electronic properties were not investigated . Note that the structurally related (indol-3-yl)phosphines are powerful ligands for Pd-catalyzed cross-coupling reactions. ,− Herein, we report the synthesis and properties of a series of (1,2,5-trimethylpyrrolyl)phosphines that, consistent with Zipse’s prediction, are strongly electron-donating arylphosphines.…”

Section: Introductionmentioning

confidence: 99%

1,2,5-Trimethylpyrrolyl Phosphines: A Class of Strongly Donating Arylphosphines

et al. 2023

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Arylphosphines are among the most important ligands in coordination chemistry and catalysis but are generally inferior to alkylphosphines when strong electron donor properties are required. Herein, we report the synthesis and properties of 1,2,5-trimethylpyrrolyl phosphines and show that their electrondonating ability can exceed that of alkylphosphines. The new phosphines can be prepared on a multi-gram scale in one-pot procedures starting from commercially available reagents. Tris-(1,2,5-trimethyl)pyrrolylphosphine P(tmp) 3 is a crystalline solid, displays a Tolman electronic parameter (TEP) of 2055.0 cm −1 and can be handled in air. Nickel(0), palladium(II), gold(I), and ruthenium(II) complexes with 1,2,5-trimethylpyrrolyl-based phosphines are reported in addition to preliminary investigations on the use of P(tmp) 3 in ruthenium-catalyzed olefin metathesis.

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Section: Introductionmentioning

confidence: 99%

1,2,5-Trimethylpyrrolyl Phosphines: A Class of Strongly Donating Arylphosphines

et al. 2023

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“…One of the main issues related to classic cross-coupling protocols concerns the use of harmful dipolar aprotic solvents such as NMP and DMF. − This class of solvents nowadays is under strict regulation because of their toxicity and environmental impact. Their impact in terms of waste production is even higher if we consider that they are often used as aqueous mixtures. , In addition, even when a solid catalyst is used in coupling reactions, amide dipolar aprotic solvents strongly bind to catalytically active metal catalysts, such as palladium, facilitating their dissolution with a consequent significant leaching into the product.…”

Section: Introductionmentioning

confidence: 99%

Sustainable Approach to Waste-Minimized Sonogashira Cross-Coupling Reaction Based on Recoverable/Reusable Heterogeneous Catalytic/Base System and Acetonitrile Azeotrope

Kozell

McLaughlin

Strappaveccia

et al. 2016

ACS Sustainable Chem. Eng.

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In this contribution, we present a chemically efficient and sustainable protocol for the palladium-catalyzed copper-free Sonogashira cross-coupling reaction, based on the use of a heterogeneous catalytic system. This consists in the combination of a palladium catalyst on highly cross-linked thiazolidine network on silica and a polystyrene-supported base. The solid catalyst/base system acts as a palladium scavenger avoiding leaching of the metal and consequent product contamination. The reaction can be conducted in safe and easily recoverable acetonitrile/water azeotrope as reaction medium. This proved to be an efficient greener alternative to the classic toxic aprotic media commonly used in cross-coupling reaction, such as DMF and NMP. Acetonitrile/water azeotrope could be easily recovered and reused allowing the minimization of waste production. Our approach, based on the use of both a supported base and a supported catalyst, has proven to be efficient for the waste reduction, as proved by the low E-factor values achieved

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“…Thus, time-consuming method development and optimization is often necessary to yield adequate overall catalyst performance . In response, the development of contemporary homogeneous Pd catalysts for the copper-free Sonogashira reaction have circumvented the drawbacks associated with the use of copper as cocatalysts. − Several notable examples for the coupling of more challenging aryl chloride substrates include contributions from Buchwald, , Beller, , Hua, − Colacot, ,, and Plenio. , …”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights and Implications of Dearomative Rearrangement in Copper-Free Sonogashira Cross-Coupling Catalyzed by Pd-Cy*Phine

et al. 2016

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The reaction mechanism for the in situ prepared Pd-Cy*Phine catalyst used in copper-free Sonogashira coupling was investigated using density functional theory. In addition, the significance of the meta-terarylphosphine ligand architecture of Cy*Phine was probed, as it had been previously shown experimentally to augment catalytic activity relative to its biarylphosphine analogue, XPhos. The calculated reaction barriers and free energies for the steps in the catalytic cycle suggest that the suppression of a dearomative rearrangement pathway is likely to be an important feature for the improved catalytic performance observed for the Pd-Cy*Phine system.

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Ferrocenyl (P,N)-diphosphines incorporating pyrrolyl, imidazolyl or benzazaphospholyl moieties: Synthesis, coordination to group 10 metals and performances in palladium-catalyzed arylation reactions

Cited by 17 publications

References 27 publications

1,2,5-Trimethylpyrrolyl Phosphines: A Class of Strongly Donating Arylphosphines

1,2,5-Trimethylpyrrolyl Phosphines: A Class of Strongly Donating Arylphosphines

Sustainable Approach to Waste-Minimized Sonogashira Cross-Coupling Reaction Based on Recoverable/Reusable Heterogeneous Catalytic/Base System and Acetonitrile Azeotrope

Mechanistic Insights and Implications of Dearomative Rearrangement in Copper-Free Sonogashira Cross-Coupling Catalyzed by Pd-Cy*Phine

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