Continuous flow homogeneous alkene metathesis with built-in catalyst separation

Duque, Rubén; Öchsner, Eva; Clavier, Hervé; Caïjo, Fréderic; Nolan, Steven P.; Mauduit, Marc; Cole‐Hamilton, David J.

doi:10.1039/c1gc15048k

Cited by 86 publications

(45 citation statements)

References 57 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Shortly later, Riisager et al published the first successful example of continuous gas-phase SILP catalysis [63]. During the last years, many technically relevant examples of SILP catalysis have been published, including examples of hydroformylation [64,65], hydrogenation [66,67], enantioselective hydrogenation [68,69], water gas shift reaction [70,71], alkene metathesis [72,73], hydroamination [74] and carbonylation of methanol [75]. Additional valuable information about SILP catalysis has been collected in reviews by Riisager et al [76,77], Gu and Li [78], van Doorslaer et al [79], and Virtanen et al [80].…”

Section: Supported Ionic Liquid Phase (Silp) Catalysismentioning

confidence: 99%

Ionic Liquids in Catalysis

2014

View full text Add to dashboard Cite

Ionic liquids (ILs), salts with melting points below 100°C, represent a fascinating class of liquid materials typically characterized by an extremely low vapor pressure. Besides their application as new solvents or as electrolytes for electrochemical purposes, there are two important concepts of using ILs in catalysis: Liquid-liquid biphasic catalysis and IL thin film catalysis. Liquid-liquid biphasic catalysis enables either a very efficient manner to apply catalytic ILs, e.g. in Friedel-Crafts reactions, or to apply ionic transition metal catalyst solutions. In both cases, phase separation after reaction allows an easy separation of reaction products and catalyst re-use. One problem of liquidliquid biphasic catalysis is mass transfer limitation. If the chemical reaction is much faster than the liquid-liquid mass transfer the latter limits the overall reaction rate. This problem is overcome in IL thin film catalysis where diffusion pathways and thus the characteristic time of diffusion are short. Here, Supported Ionic Liquid Phase (SILP) and Solid Catalyst with Ionic Liquid Layer (SCILL) are the two most important concepts. In both, a high surface area solid substrate is covered with a thin IL film, which contains either a homogeneously dissolved transition metal complex for SILP, or which modifies catalytically active surface sites at the support for SCILL. In each concept, interface phenomena play a very important role: These may concern the interface of an IL phase with an organic phase in the case of liquidliquid biphasic catalysis. For IL thin film catalysis, the interfaces of the IL with the gas phase and with catalytic nanoparticles and/or support materials are of critical importance. It has recently been demonstrated that these interfaces and also the bulk of ILs can be investigated in great detail using surface science studies, which greatly contributed to the fundamental understanding of the catalytic properties of ILs and supported IL materials. Exemplary results concerning the IL/vacuum or IL/gas interface, the solubility and surface enrichment of dissolved metal complexes, the IL/support interface and the in situ monitoring of chemical reactions in ILs are presented.

show abstract

Section: Supported Ionic Liquid Phase (Silp) Catalysismentioning

confidence: 99%

Ionic Liquids in Catalysis

2014

View full text Add to dashboard Cite

show abstract

“…208 Finally, a variety of reactions can be achieved by the mean of continuous flow Chemistry, such as hydroformylation 216 and alkene metathesis. 177 According to Seeberger, micro-reactors are the round bottom flask of this new century. 211 …”

Section: General Overview On Continuous Flow Chemistrymentioning

confidence: 99%

“…In order to improve the atom efficiency for obtaining shorter chain diesters from methyl oleate and related compounds, the metathesis of methyl oleate with dimethyl maleate to produce dimethyl 1,11-undec-2-endioate, a C 11 diester and methyl 2-undecenoate, an α,β-unsaturated ester, was proposed and demonstrated. 177 In order to make the C 12 diester, we attempted the methoxycarbonylation of methyl 2-undecenoic acid, which requires the double bond to move eight bonds into the least thermodynamically favoured position before being trapped there by methoxycarbonylation. Previously the maximum distance for isomerisation that we had observed in this Chemistry was 8 bonds (for methyl oleate [64][65][66][67]140,141 or methyl erucate 66,67,141 ) or 7 bonds where the double bond was conjugated to an ester (second carbonylation of 1-octyne to give dimethyl 1,10-decanedioate).…”

Section: Shorter Diesters From Natural Resourcesmentioning

confidence: 99%

Polymer precursors from catalytic reactions of natural oils

et al. 2012

Self Cite

View full text Add to dashboard Cite

Dimethyl 1,19-nonadecanedioate is produced from the methoxycarbonylation of commercial olive, rapeseed or sunflower oils in the presence of a catalyst derived from [Pd 2 (dba) 3 ], bis(ditertiarybutylphosphinomethyl)benzene (BDTBPMB) and methanesulphonic acid (MSA). The diester is then hydrogenated to 1,19-nonadecanediol using Ru/1,1,1-tris-(diphenylphosphinemethyl)ethane (triphos). 1,19-Nonadecadienoic acid is hydrogenated to short chain oligoesters, which can themselves be hydrogenated to 1,19-nonadecanol by hydrogenation in the presence of water.

show abstract

“…Finally, the catalytic solid could be reused up to six times with similar yields provided the reaction time was extended from 1 to 2 h. This process was extended to catalyst C4 and to the synthesis of macrocyclic lactones affording 13-to 18-membered lactones in satisfactory yields [87]. Another original use of a SILC consisted in a continuous flow process as reported in 2010 [88]. Catalyst C8 was immobilized in [bmim][NTf 2 ] and supported within the pores of silica with supercritical CO 2 as the flowing medium.…”

Section: Supported Ionic Liquid Phase and Catalystmentioning

confidence: 98%

RTILs in Catalytic Olefin Metathesis Reactions

Fischmeister¹,

Bruneau²

2013

Ionic Liquids (ILs) in Organometallic Catalysis

View full text Add to dashboard Cite

International audienceThe homogeneous catalytic olefin metathesis reaction has found a tremendous interest in the past 20 years and multiple applications have now emerged in fine chemical synthesis and polymer chemistry. Immobilization of olefin metathesis (pre)catalysts in room temperature ionic liquids (RTILs) offers the opportunity to recover and in some cases reuse the catalyst and it is also a practical way to reduce the level of metal contaminants in the desired products. This chapter covers the research in this field from the early days with an emphasis on recent results and with a critical look at the origin of catalyst recycling

show abstract

Continuous flow homogeneous alkene metathesis with built-in catalyst separation

Cited by 86 publications

References 57 publications

Ionic Liquids in Catalysis

Ionic Liquids in Catalysis

Polymer precursors from catalytic reactions of natural oils

RTILs in Catalytic Olefin Metathesis Reactions

Contact Info

Product

Resources

About