Effective one-pot synthesis of (<i>E</i>)-poly(vinyl arylenes) <i>via</i> trans-borylation/Suzuki coupling protocol

Szyling, Jakub; Walkowiak, Jędrzej

doi:10.1515/gps-2016-0217

Cited by 3 publications

(1 citation statement)

References 37 publications

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“…Our research interest perfectly matches the above-described area because we are focused on the synthesis and catalytic transformation of organoboron and organosilicon compounds performed in the presence of molecular catalysts and in one-pot procedures, immobilization of molecular catalysts, the use of nonconventional media, and separation techniques, e.g., IL, scCO 2 . − …”

Section: Introductionmentioning

confidence: 82%

Recyclable Hydroboration of Alkynes Using RuH@IL and RuH@IL/scCO₂ Catalytic Systems

Szyling

Franczyk

Stefanowska

et al. 2018

ACS Sustainable Chem. Eng.

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This paper reports on the first detailed studies on green and sustainable methods for the repetitive batch hydroboration of terminal and internal alkynes by the effective immobilization of Ru(CO)Cl(H)(PPh3)3 in various ionic liquids (RuH@IL) or in biphasic ionic liquid/supercritical CO2 (RuH@IL/scCO2) systems. The systems RuH(1 mol %)@[EMPyrr][OTf](IL8) and RuH(1 mol %)@[EMPyrr][NTf2](IL9) were found to be the most effective immobilization approaches, with both allowing the completion of over 10 complete catalytic cycles in the hydroboration of a series of different alkynes. An increase in the catalyst content to 2 mol % (RuH(2 mol %)@[EMPyrr][NTf2](IL9)) allowed for the completion of 25 repetitive batches, which proved the high utility of the developed system. In each case, high yields of products were obtained, and their purity was confirmed through NMR, MS, and ICP techniques. On the other hand, the use of RuH(1 mol %)@/[EMPyrr][OTf](IL8)/scCO2 in the hydroboration of phenylacetylene with pinacolborane, permitted effective completion of 8 cycles, at a much lower temperature than that at which RuH@IL was used (40 vs 100 °C). Moreover, the application of such a system has a positive impact on the environment and process sustainability via the exchanging of organic solvent for scCO2 used for product extraction and separation when working with RuH@IL. The strategies presented in this work are, so far, the most effective and recyclable systems based on ILs for the hydroboration of alkynes with high TONs. In the future, they will be applied in continuous flow regime.

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Section: Introductionmentioning

confidence: 82%

Recyclable Hydroboration of Alkynes Using RuH@IL and RuH@IL/scCO₂ Catalytic Systems

Szyling

Franczyk

Stefanowska

et al. 2018

ACS Sustainable Chem. Eng.

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A recyclable Ru(CO)Cl(H)(PPh₃)₃/PEG catalytic system for regio‐ and stereoselective hydroboration of terminal and internal alkynes

et al. 2018

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This paper reports on the first repetitive batch selective hydroboration of terminal and internal alkynes in a series of poly(ethylene glycols) (PEGs), used as solvents and media for the immobilization of a Ru(CO)Cl(H)(PPh3)3 catalyst. The system based on 2 mol% of Ru−H complex and poly(ethylene glycol) with α‐methyl/ω‐trimethylsilyl ending groups (Mw=2000) was found to be the most efficient, and was able to carry out over 19 complete runs with the Z‐addition of pinacolborane to the phenylacetylene. With the use of one portion of the developed catalytic system, the hydroboration of five different alkynes was performed consecutively, and led to five different products being obtained with high yields and purities. The developed strategy was characterized by high TON values and it was found to be the best recyclable protocol, leading to alkenyl boronates in all reported cases.magnified image

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Ru-Catalyzed Repetitive Batch Borylative Coupling of Olefins in Ionic Liquids or Ionic Liquids/scCO2 Systems

et al. 2020

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The first, recyclable protocol for the selective synthesis of (E)-alkenyl boronates via borylative coupling of olefins with vinylboronic acid pinacol ester in monophasic (cat@IL) or biphasic (cat@IL/scCO2) systems is reported in this article. The efficient immobilization of [Ru(CO)Cl(H)(PCy3)2] (1 mol%) in [EMPyr][NTf2] and [BMIm][OTf] with the subsequent extraction of products with n-heptane permitted multiple reuses of the catalyst without a significant decrease in its activity and stability (up to 7 runs). Utilization of scCO2 as an extractant enabled a significant reduction in the amount of catalyst leaching during the separation process, compared to extraction with n-heptane. Such efficient catalyst immobilization allowed an intensification of the processes in terms of its productivity, which was indicated by high cumulative TON values (up to 956) in contrast to the traditional approach of applying volatile organic solvents (TON = ~50–100). The reaction was versatile to styrenes with electron-donating and withdrawing substituents and vinylcyclohexane, generating unsaturated organoboron compounds, of which synthetic utility was shown by the direct transformation of extracted products in iododeborylation and Suzuki coupling processes. All synthesized compounds were characterized using 1H, 13C NMR and GC-MS, while leaching of the catalyst was detected with ICP-MS.

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Effective one-pot synthesis of (E)-poly(vinyl arylenes) via trans-borylation/Suzuki coupling protocol

Abstract: A new stereoselective method for the synthesis of (

Cited by 3 publications

References 37 publications

Recyclable Hydroboration of Alkynes Using RuH@IL and RuH@IL/scCO₂ Catalytic Systems

Recyclable Hydroboration of Alkynes Using RuH@IL and RuH@IL/scCO₂ Catalytic Systems

A recyclable Ru(CO)Cl(H)(PPh₃)₃/PEG catalytic system for regio‐ and stereoselective hydroboration of terminal and internal alkynes

Ru-Catalyzed Repetitive Batch Borylative Coupling of Olefins in Ionic Liquids or Ionic Liquids/scCO2 Systems

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Effective one-pot synthesis of (E)-poly(vinyl arylenes) via trans-borylation/Suzuki coupling protocol

Abstract: A new stereoselective method for the synthesis of (

Cited by 3 publications

References 37 publications

Recyclable Hydroboration of Alkynes Using RuH@IL and RuH@IL/scCO2 Catalytic Systems

Recyclable Hydroboration of Alkynes Using RuH@IL and RuH@IL/scCO2 Catalytic Systems

A recyclable Ru(CO)Cl(H)(PPh3)3/PEG catalytic system for regio‐ and stereoselective hydroboration of terminal and internal alkynes

Ru-Catalyzed Repetitive Batch Borylative Coupling of Olefins in Ionic Liquids or Ionic Liquids/scCO2 Systems

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Product

Resources

About

Recyclable Hydroboration of Alkynes Using RuH@IL and RuH@IL/scCO₂ Catalytic Systems

Recyclable Hydroboration of Alkynes Using RuH@IL and RuH@IL/scCO₂ Catalytic Systems

A recyclable Ru(CO)Cl(H)(PPh₃)₃/PEG catalytic system for regio‐ and stereoselective hydroboration of terminal and internal alkynes