High efficiency of cavity-based triaryl-phosphines in nickel-catalysed Kumada–Tamao–Corriu cross-coupling

Monnereau, Laure; Sémeril, David; Matt, Dominique

doi:10.1039/c0cc05805j

Cited by 41 publications

(16 citation statements)

References 32 publications

(28 reference statements)

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“…In the corresponding intermediates, in which the metal–arene fragment is entrapped in the calixarene, the ligand crowding is significantly increased with respect to that of related complexes that have the metal exo ‐bonded. As a result, the proportion of monoligated intermediates of the type [(L)Pd 0 (η 2 ‐ArX)] increases with respect to that of related bis(phosphane) complexes , . Monophosphane Pd 0 complexes are known to undergo oxidative addition (the rate‐determining step with Pd) faster than the corresponding bis(phosphane) complexes.…”

Section: Resultsmentioning

confidence: 99%

“…We have recently investigated the properties of some conical calix[4]arenes bearing a diarylphosphino group tethered at their upper rim. These have been tested in palladium‐catalysed Suzuki–Miyaura and nickel‐catalysed Kumada–Tamao–Corriu cross‐coupling reactions . They showed considerably higher activities than conventional triarylphosphanes.…”

Section: Introductionmentioning

confidence: 99%

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Catalytic Behaviour of Calixarenylphosphanes in Nickel‐Catalysed Suzuki–Miyaura Cross‐Coupling

et al. 2016

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Catalytic Behaviour of Calixarenylphosphanes in Nickel‐Catalysed Suzuki–Miyaura Cross‐Coupling

et al. 2016

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“…[15][16][17][18][19] Bulkiness and basicity are two key features in these catalysed reactions. [20,21] As an extension of our studies on monophosphines based on cone-shaped macrocycles, [22][23][24][25] we now describe the synthesis of two bulky phosphines, both based on a resorcinarene cavitand, as well as their use in palladium-catalysed Suzuki-Miyaura cross-coupling reactions of aryl chlorides and bromides. Bulky ligands are furthermore known to efficiently promote the reductive elimination process.…”

Section: Introductionmentioning

confidence: 99%

Resorcinarenyl‐Phosphines in Suzuki–Miyaura Cross‐Coupling Reactions of Aryl Chlorides

et al. 2014

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Two phosphines built on a bowl-shaped resorcin[4]arene skeleton, namely 5-diphenylphosphanyl-and 5-diisopropylphosphanyl-4(24),6(10),12 (16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentylresorcin[4]arene, have been synthesised and tested in the Suzuki-Miyaura cross-coupling reaction of aryl halides. Combining these ligands with [Pd(OAc) 2 ] resulted in highly active catalysts that allowed the formation of o,oЈ-biphenyls starting from aryl chlorides. The remarkable [a]1364 activities observed possibly arise from 1) the capacity of the phosphines to operate transiently as P,O chelators, thereby increasing the electron density of the metal, and 2) the ability of the ligands to embed metal-organic units, which, when occurring, makes the ligand considerably bulkier so as to disfavour the coordination of a second phosphine. Both features are known to facilitate the oxidative addition step.

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“…Calixarenes are valuable synthons for the construction of receptor ligands and/or of sterically demanding ligands. [17][18][19] Scheme 1. The two low-energy mesomeric forms of an iminophosphorane.…”

Section: Introductionmentioning

confidence: 99%

Calixarene‐Derived Mono‐Iminophosphoranes: Highly Efficient Ligands for Palladium‐ and Nickel‐Catalysed Cross‐Coupling

2013

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The first mono-iminophosphoranes based on a calix[4]arene skeleton have been synthesised and tested in the arylation of aryl bromides and aryl chlorides. Combining these ligands with [·mol(M) À1 ·h À1 were obtained in each case. The remarkable activities observed probably arise from the ligands ability to form complexes with cavity-entrapped "MArX" moieties (endo-complexes), their highly crowded metal environment fa-vouring formation of mono-ligated intermediates over that of less reactive bis-ligated ones. Possible supramolecular interactions within the cavity involving the receptor wall and the aromatic substrate may also significantly influence the reaction rates, notably by increasing the proportion of endo-complexes.Staudinger condensation [20] of calixarenyl-phosphine 1 with aryl azides 2-6 led quantitatively to the iminophosphorane-calix[4]arenes 7-11, respectively (Scheme 2). Their formation was confirmed by MALDI-TOF analysis, each mass spectrum being characterised by a single peak with the isotopic pat-tern exactly as expected for the corresponding [M + H] + ion. The 31 P NMR spectra all displayed a singlet appearing in a range (À11-0 ppm) that is typical for iminophosphoranes. [7] Each 1 H NMR spectrum was consistent with a C s -symmetrical molecule. The conical conformation of the calix[4]arene moieties was inferred from the 13 C NMR spectra, in which the two ArCH 2 Ar signals appeared at ca. 31 ppm. [21] The synthesised iminophosphoranes were only moderately stable when not kept under nitrogen, their reaction with air leading quantitatively after few hours to phosphine oxide 12 and the corresponding aniline derivative.The five iminophosphoranes were found to be suitable for metal binding (Scheme 3). For example, iminophosphorane 9 gave quantitatively complex 13

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High efficiency of cavity-based triaryl-phosphines in nickel-catalysed Kumada–Tamao–Corriu cross-coupling

Cited by 41 publications

References 32 publications

Catalytic Behaviour of Calixarenylphosphanes in Nickel‐Catalysed Suzuki–Miyaura Cross‐Coupling

Catalytic Behaviour of Calixarenylphosphanes in Nickel‐Catalysed Suzuki–Miyaura Cross‐Coupling

Resorcinarenyl‐Phosphines in Suzuki–Miyaura Cross‐Coupling Reactions of Aryl Chlorides

Calixarene‐Derived Mono‐Iminophosphoranes: Highly Efficient Ligands for Palladium‐ and Nickel‐Catalysed Cross‐Coupling

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