Supercritical Fluids as Advanced Media for Reaction and Separation in Homogeneous Catalysis

Walkowiak, Jędrzej; Franciò, Giancarlo; Leitner, Walter

doi:10.1002/9783527651733.ch20

Cited by 5 publications

(4 citation statements)

References 178 publications

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“…Isolated yield: 81%.NMR and GC-MS data are in agreement with the literature [29]. (9), 171 (7), 158(51), 143(100), 128 (41), 117(51), 105 (12), 91 (19), 77 (8), 57 (7). Isolated yield: 79%.…”

Section: Iododeborylation Of 3a With Molecular Iodinesupporting

confidence: 87%

“…C α to boron atom was not observed. MS (EI) [m/z (%)]: 230(M + , 29), 215 (21), 187 (11), 173 (8), 157 (14), 144(83), 129(100), 118 (14), 105 (33), 77 (19). Isolated yield: 81%.…”

Section: Iododeborylation Of 3a With Molecular Iodinementioning

confidence: 99%

“…C α to boron atom was not observed. MS (EI) [m/z (%)]: 244(M + , 32), 229 (12), 171 (13), 158 (45), 143(100), 128 (31), 117(49), 105 (11), 91(112), 77 (8), 57 (10). Isolated yield: 69%.…”

Section: Iododeborylation Of 3a With Molecular Iodinementioning

confidence: 99%

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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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Section: Iododeborylation Of 3a With Molecular Iodinesupporting

confidence: 87%

“…C α to boron atom was not observed. MS (EI) [m/z (%)]: 230(M + , 29), 215 (21), 187 (11), 173 (8), 157 (14), 144(83), 129(100), 118 (14), 105 (33), 77 (19). Isolated yield: 81%.…”

Section: Iododeborylation Of 3a With Molecular Iodinementioning

confidence: 99%

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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 negligible solubility of ILs in scCO 2 results in the use of these solvents in repetitive batch and continuous flow processes. In such systems, the catalyst is immobilized in IL, maintaining its homogeneous character, while reagents and products are transported by CO 2 . − The limitation of the application of such catalyst system results from the volatility of reagents and their polarity. They need to be highly volatile to be easily extracted from the reactor.…”

Section: Introductionmentioning

confidence: 99%

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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Recycling of Catalysts from Surfactant Systems

Schwarze

2020

Chemie Ingenieur Technik

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This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. Dedicated to Prof. Dr.-Ing. Matthias Kraume on the occasion of his 65th birthday Surfactant systems belong to the green solvents and can be used as reaction media for very different stoichiometric and catalytic reactions. The possibilities to separate catalysts and products afterward are very diverse. This overview article illustrates the different possibilities, with selected examples. There is no general separation concept, but the separation method has to be chosen according to the selected reaction system.

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Supercritical Fluids as Advanced Media for Reaction and Separation in Homogeneous Catalysis

Cited by 5 publications

References 178 publications

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

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

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

Recycling of Catalysts from Surfactant Systems

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Supercritical Fluids as Advanced Media for Reaction and Separation in Homogeneous Catalysis

Cited by 5 publications

References 178 publications

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

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

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

Recycling of Catalysts from Surfactant Systems

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Product

Resources

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