Advances in thermomorphic liquid/liquid recycling of homogeneous transition metal catalysts

Behr, Arno; Henze, Guido; Johnen, Leif; Awungacha, Colin

doi:10.1016/j.molcata.2008.01.021

Cited by 82 publications

(55 citation statements)

References 8 publications

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“…47 In the chosen reactions, phenylboronic acid and base are soluble in the lower aqueous phase, bromoacetophenone or the product 4-acetylbiphenyl is dissolved in the top heptane phase, whereas the transition metal catalyst—either in a well-defined molecular state, or as a nanoparticle dispersion—is preferentially located in the intermediate bicontinuous microemulsion layer (Figure 7). …”

Section: Resultsmentioning

confidence: 99%

Ionic Liquid-Based Microemulsions in Catalysis

et al. 2016

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Section: Resultsmentioning

confidence: 99%

Ionic Liquid-Based Microemulsions in Catalysis

et al. 2016

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“…3,4 Various amines can be synthesized in a simple, efficient and atom-economic way by performing a hydroaminomethylation reaction (HAM). [10][11][12][13][14][15][16][17] Highlights of the recent advantages are applications on natural products, 18 direct synthesis of drugs [19][20][21] and monomers for plastics, 22 isomerization and hydroaminomethylation of internal olens to linear amines, 23,24 catalyst recycling approaches by immobilization 25,26 or two-phase techniques 27,28 and mechanistic insights. In the rst step, a hydroformylation of an olen is performed followed by the condensation of the resulting aldehyde with a primary or secondary amine to give the corresponding enamine or imine with water as a byproduct.…”

Section: Introductionmentioning

confidence: 99%

Rhodium-catalyzed hydroaminomethylation of cyclopentadiene

2015

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A one-step rhodium catalyzed direct route from cyclopentadiene (Cpd) to saturated C 6 -amines is presented via hydroaminomethylation (HAM). The homogeneous catalyst of Rh(II) octanoate dimer without additional phosphorus ligands was established giving a 77% yield of the monoamine species of Cpd with pyrrolidine within 4 hours. The unwanted reaction of Cpd, the dimerization to dicyclopentadiene (Dcpd), could be suppressed by careful adjustment of the CO : H 2 ratio in the synthesis gas and the choice of solvent, both giving the possibility to steer the reaction to selectively produce amines of either Cpd or Dcpd. Furthermore, other investigated cyclic and non-cyclic aliphatic amine substrates showed excellent selectivity up to 100% for the formation of the HAM-products. CH 3 ); 2.80 (m, 2H, 2CH); 2.21-2.24 (m, 1H, CH); 2.16 (d, 3 J ( 1 H-1 H) ¼ 8 Hz, 2H, CH 2 ), 1.96-2.00 (m, 1H, CH); 1.88-1.92 (m, 2H, 2CH); 1.80 (m, 2H, 2CH); 1.65-1.71 (m, 4H, 2CH 2 ); 1.78-1.82 (m, 2H, 2CH) 1.43-1.53 (m, 4H, 2CH 2 ); 1.10-1.15 (m, 2H, 2CH). 13 C( 1 H) (125.77 MHz, CDCl 3 , TMS) d 13 C [ppm]: 175.95 (s, 1C); 60668 | RSC Adv., 2015, 5, 60667-60673 This journal is Scheme 1 Product range in the hydroaminomethylation of Cpd 1 with pyrrolidine.This journal is

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“…This is achieved by using two different liquid phases, an organic phase, and a perfluorinated phase [8,9]. The temperature-dependent miscibility of perfluorinated liquids with common organic solvents allows the establishment of a system in which the catalytic reaction takes place in a homogeneous phase at higher temperatures and where the catalyst separation occurs in a heterogeneous system at lower temperatures [10][11][12][13][14].…”

Section: Introductionmentioning

confidence: 99%

Palladium-Catalyzed Carbon-Carbon Cross-Coupling Reactions in Thermomorphous Double Emulsions

Misuk¹,

Mai²,

Γιαννόπουλος³

et al. 2015

J Flow Chem

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The method of combining the concept of fluorous biphasic catalysis (FCB) with micro multiple emulsions benefits from the advantages of homogeneous as well as from heterogeneous catalysis in continuous micro flow. In this particular case, three immiscible fluid phases in continuous micro segmented flow were used to perform palladium-catalyzed Heck crosscoupling reactions of styrene with aryl halides. A capillary tube-in-tube coaxial flow setup in combination with a glass micro reactor was used to produce monodisperse aqueous phase/organic phase/perfluorinated phase double emulsions. The resulting emulsions had a core-shell droplet structure composed of a perfluorcarbon fluid in which a palladium catalyst with fluorinated phosphine ligands was dissolved, an organic phase consisting of a solvent and two reagents, and an alkaline aqueous solution. The fluorous and organic phases of the double emulsion form a thermomorphous system which can be converted into one phase by an increase of temperature above 150°C, and the catalytic reaction is performed temporarily. By decreasing the temperature, a phase separation takes place; after that, the organic phase contains the product and the catalyst is located in the fluorous phase. The separated catalyst solution was reused several times without a noticeable loss of activity. The main advantage of this method is to use temporarily very high catalyst concentrations in each droplet, while employing only small amounts of the catalyst for the overall reaction volume.

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Advances in thermomorphic liquid/liquid recycling of homogeneous transition metal catalysts

Cited by 82 publications

References 8 publications

Ionic Liquid-Based Microemulsions in Catalysis

Ionic Liquid-Based Microemulsions in Catalysis

Rhodium-catalyzed hydroaminomethylation of cyclopentadiene

Palladium-Catalyzed Carbon-Carbon Cross-Coupling Reactions in Thermomorphous Double Emulsions

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