A recyclable nanosize aminoarenethiolato copper(I) catalyst for C–C coupling reactions

Arink, Anne M.; Coevering, Rob van de; Wieczorek, Birgit; Firet, Judith J.; Jastrzebski, Johann T. B. H.; Gebbink, Robertus J. M. Klein; Koten, Gerard van

doi:10.1016/j.jorganchem.2004.07.023

Cited by 10 publications

(5 citation statements)

References 26 publications

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“…After reaction the dialysis bag(s) can be easily removed from the reaction mixture and in principle be placed into a fresh reaction solution. Proofs of concept for such a 'teabag' approach have been reported earlier by us 25, 26 and more recently by Gade. 27 A prerequisite for the separation and recycling of dendritic catalysts is that the active catalytic centers should be tightly bound to the dendritic support to prevent catalyst leaching.…”

Section: Introductionmentioning

confidence: 68%

SCS-pincer palladium-catalyzed auto-tandem catalysis using dendritic catalysts in semi-permeable compartments

et al. 2011

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Novel monometallic and dendritic SCS-pincer palladium complexes 2, 3 and 4 have been synthesized in good yields (60-89%) and high purity (palladium loading >97%). These complexes were successfully used as catalysts in the stannylation of cinnamyl chloride with hexamethylditin and in the catalytic auto-tandem reaction consisting of this stannylation followed by an electrophilic addition with 4-nitrobenzaldehyde, showing similar reaction rates and selectivities for all complexes. Dendritic complex 4 has furthermore been used in the compartmentalized catalysis of single and auto-tandem reactions, allowing catalyst reuse for four consecutive runs.

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Section: Introductionmentioning

confidence: 68%

SCS-pincer palladium-catalyzed auto-tandem catalysis using dendritic catalysts in semi-permeable compartments

et al. 2011

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“…Although this was not exhaustively explored in this study, the size of this molecularly enlarged ligand would allow for its separation from the reaction mixture by means of nanofiltration using a membrane with MWCO lower than 1000 Da. 20 Overall, this study has shown the delicacy in designing the proper soluble supporting material for single-site homogeneous catalysts. Where earlier we had shown that proximity effects can be detrimental for the catalytic activity of preformed catalysts, 16b the current study has shown that care should be taken in the immobilization of chiral ligands used for the in situ formation of catalysts.…”

Section: Discussionmentioning

confidence: 90%

“…Most of the relevant publications in the field emphasize on the fact that the commercial membranes are often not compatible with organic solvents required for the reported catalytic transformations (olefin metathesis, cross-coupling etc.) 19,20 and in some cases the membrane material interacts with a catalyst, causing its deactivation. 14 Especially when using hydrogen peroxide the membrane choice is limited.…”

Section: Catalyst Recycling Studiesmentioning

confidence: 99%

Molecularly enlarged S,S-BnTsDPEN ligands for iron-catalyzed asymmetric olefin epoxidation reactions using hydrogen peroxide

Yazerski

Orue

Evers

et al. 2013

Catal. Sci. Technol.

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A convenient approach for the anchoring of S,S-BnTsDPEN ligands (S,S-N-tosyl-1,2-diphenylethylenediamine) to branched carbosilane scaffolds was investigated. It is based on a high-yielding reductive amination reaction between commercially available S,S-TsDPEN and readily accessible carbosilanes furnished with benzaldehyde terminal fragments. These molecularly enlarged ligands, bearing four S,S-BnTsDPEN units, and their simplified monomeric and ''dimeric'' analogues were evaluated in iron(III)-catalyzed asymmetric trans-stilbene epoxidation reactions using hydrogen peroxide as an environmentally benign oxidant. The catalytic investigations showed a large degree of variation in the activity and stereoselectivity of the series of DPEN catalysts. In combination with ESI-MS investigations, these data revealed an important role of the ligand orientation in determining the overall activity of the catalyst system. Accordingly, a suitable design of the molecularly enlarged ligands resulted in fully retained activity and selectivity in catalysis. Finally, a number of strategies for the recovery and reuse of the best performing carbosilane-tethered DPEN ligands were explored.

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“…Note that in this case exclusively 1-lithiation is possible and indeed occurs quantitatively. From this reaction (see Supporting Information S10), a pale yellow crystalline material was obtained with a [3-(SiMe 3 )-2-(Me 2 NCH 2 )C 10 H 5 Li-1] 2 ·OEt 2 ( 3 ) empirical stoichiometry ( 1 H and 13 C NMR) . The structure of 3 in the solid (confirmed via X-ray crystal structure determination, vide infra) is schematically shown in Scheme .…”

Section: Resultsmentioning

confidence: 99%

Directed ortho-Lithiation: Observation of an Unexpected 1-Lithio to 3-Lithio Conversion of 1-Lithio-naphthyllithium Compounds with an ortho-Directing 2-(Dimethylamino)methyl Group

et al. 2013

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Regioselectivity is an important aspect in the design of organic protocols involving Directed ortho-Lithiation (DoL) of arenes, in particular with those arenes containing heteroatom substituents as directing groups. The DoL of 2-[(dimethylamino)methyl]naphthalene (dman) that proceeds with low regioselectivity was revisited by varying both the nature of the lithiating reagent (either n-BuLi or t-BuLi) and/or the solvent (pentane or diethyl ether); the 3-deuterated substrate, 3-Ddman, was also investigated as a substrate to compare to that of dman. The 3-lithio regioisomer exists as tetranuclear [2-(Me2NCH2)C10H6Li-3]4, 1, both in the solid state (X-ray) and in solution (NMR). The 1-lithio regioisomer, 2a, is insoluble; in the presence of additional coordinating solvents (Et2O) or ligands (dman), it exists as dinuclear [2-(Me2NCH2)C10H6Li-1]2·L (coordinated L = Et2O: 2b, dman: 2c) in apolar solvents. Heating solutions of 2c in toluene-d8 (to 90 °C) induced a surprisingly clean and quantitative 1-lithio to 3-lithio conversion of the 1-lithio-naphthalene isomer. This type of reaction is rare in organolithium chemistry and has obvious significant implications for the design of regioselective DoL protocols; this thus represents the synthetically useful protocol for the DoL of dman in a one-pot/two-step process in toluene solution. The results of the use of 3-Ddman in these reactions gives strong credence to a mechanism involving formation of the heteroleptic species [(2-(Me2NCH2)C10H6-1)(2-(Me2NCH2)C10H6-3)Li2]·[dman], A, as the key intermediate. Intramolecular trans-lithiation takes place with A; dman becomes selectively lithiated at its 3-position, while the formerly 1-lithio-naphthalene fragment, acting as a highly unusual ortho-lithiating reagent, is converted into the N-coordinated amine, dman. In this intramolecular DoL process, free dman can be considered to act as a catalyst.

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A recyclable nanosize aminoarenethiolato copper(I) catalyst for C–C coupling reactions

Cited by 10 publications

References 26 publications

SCS-pincer palladium-catalyzed auto-tandem catalysis using dendritic catalysts in semi-permeable compartments

SCS-pincer palladium-catalyzed auto-tandem catalysis using dendritic catalysts in semi-permeable compartments

Molecularly enlarged S,S-BnTsDPEN ligands for iron-catalyzed asymmetric olefin epoxidation reactions using hydrogen peroxide

Directed ortho-Lithiation: Observation of an Unexpected 1-Lithio to 3-Lithio Conversion of 1-Lithio-naphthyllithium Compounds with an ortho-Directing 2-(Dimethylamino)methyl Group

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