Semi-continuous nanofiltration-coupled Heck reactions as a new approach to improve productivity of homogeneous catalysts

Nair, Dinesh; Scarpello, Justin T.; White, Lloyd S.; Santos, L. M. Freitas dos; Vankelecom, Ivo F.J.; Livingston, Andrew G.

doi:10.1016/s0040-4039(01)01734-8

Cited by 102 publications

(52 citation statements)

References 28 publications

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“…[3] Palladium complexes which contain sterically hindered α-diimine ligands are highly efficacious for olefin polymerization [1,2] and also for Suzuki cross-coupling reactions. [4] We are interested in Pd-catalyzed carbon-carbon coupling reactions of the Heck and Suzuki type, which are also used in fine chemical synthesis, even though currently heterogeneous catalysts are preferred. [5,6] In this work we wish to report on the synthesis and characterization of a series of palladium complexes which contain different side groups and to attempt to correlate the disparity of catalytic activity with these groups.…”

Section: Introductionmentioning

confidence: 99%

Ligand effects in palladium‐catalyzed Suzuki and Heck coupling reactions

Hanhan

2008

Applied Organom Chemis

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A range of sterically hindered diimine ligands and their palladium (II) complexes were synthesized. These compounds were fully characterized by elemental analysis, 1 H and 13 C-NMR spectroscopy. The use of the palladium complexes as catalysts for Suzuki and Heck coupling has been studied in an attempt to demonstrate the effect of side groups on catalytic activity. It was clearly seen that the location of side -CH 3 groups which bound to benzene ring had little effect on catalytic activity. Interestingly when we changed these -CH 3 groups with -Cl groups the activity of the complexes increased. On the other hand, side groups which bound to imine nitrogen also had a large effect on catalytic activity.

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Section: Introductionmentioning

confidence: 99%

Ligand effects in palladium‐catalyzed Suzuki and Heck coupling reactions

Hanhan

2008

Applied Organom Chemis

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“…Various studies at laboratory scale have been published dealing with the retention of homogeneous organometallic catalysts and recycling by organic nanofiltration (OSN) most often in methanol or other polar solvents: CoJacobsen (4 cycles) [11], Heck (5 cycles) and Suzuki (10 cycles) reaction catalysts [12,13] and more rarely in an aromatic solvent (toluene) as for Hoveyda catalysts for the olefin metathesis [14]. However, to be widely used on an industrial scale, the NF in organic medium faces several challenges.…”

Section: The Challenges Ahead For Organic Nfmentioning

confidence: 99%

Interests and challenges of organic solvent nanofiltration for sustainable chemistry: the case of homogeneous catalysis of metathesis

Rabiller-Baudry¹,

Nasser²,

Delaunay³

et al. 2011

WIT Transactions on Ecology and the Environment

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The development of chemical reactions catalysed by homogeneous organometallic complexes has allowed a significant breakthrough in synthesis chemistry, but now research axes must integrate catalysts recycling at the early stage of their conception. Catalyst recycling by nanofiltration in organic solvent (OSN) may represent an innovative route since this separation process at a molecular level is a low energy consumer. Challenges for OSN are membrane stability in organic solvents and the mastering of filtration conditions. Molecular engineering of catalysts based on slight structural modifications is also proposed to associate activity and high retention for OSN recycling. This paper deals with the integration of OSN within the homogeneous catalytic olefin metathesis reaction.

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“…A lot of research has been done to heterogenize TMCs with different techniques such as encapsulation, interphase chemistry, phase-tagging for biphasic catalysis or ionic liquids and various techniques for the immobilization of molecular catalysts on solid or colloidal supports [4]. For example, Gröschel et al [5], employed a catalytically active membrane based on poly(acrylic acid) networks containing palladium nanoparticles for the partial hydrogenation of propyne.…”

Section: Introductionmentioning

confidence: 99%

“…2001 [4], who performed a semi-continuous nanofiltration-coupled catalysis for a well-known Heck coupling reaction. They permeated the post-reaction mixture through a polyimide OSN membrane achieving an overall 90 % catalyst retention after four catalyst recycles (five reactionfiltration sequences) and a total catalyst turnover number (TON, moles of product synthesised per mol catalyst added) of 1200; Datta, et al, 2003 [8], developed catalysts for the Heck, Sonogashira and Suzuki type coupling reactions, which were retained by poly(dimethylsiloxane) (PDMS) membranes (retention higher than 99.5 %) but the catalysts lost activity after a series of catalyst recycles; Aerts, et al, 2006 [1], who used silicon-based OSN-membranes to recycle the Co-Jacobsen catalyst four times in diethylether (Et 2 O), achieving 98.5 % retention and a minor decrease in the conversion from one cycle to another; Janssen et.…”

Section: Introductionmentioning

confidence: 99%