Hydroformylation in perfluorinated solvents; improved selectivity, catalyst retention and product separation

Ruthenium-catalysed asymmetric hydrogenation with fluoroalkylated BINAP ligands in supercritical CO2

“…We have been investigating the application of perfluoroalkylated phosphorus(III) ligands for catalysis under fluorous biphase conditions [12][13][14][15][16] and in scCO 2 [5,17,18], and have synthesised a series of fluoroalkylated binaphthyl-based chiral ligands, aiming to confer solubility on these catalysts based on these ligands for use in scCO 2 (Scheme 1) [5][6][7]. Herein we detail our results on the asymmetric hydrogenation of dimethyl itaconate using ruthenium and the ligands 2 and 3 as catalyst.…”

Design and Assembly of Virtual Homogeneous Catalyst Libraries –Towards in silico Catalyst Optimisation

“…Furthermore, it is one of the few examples where homogeneous catalysis is practiced on a large industrial scale. The Rhcatalysed variation has been extensively studied under a variety of conditions, [23,24] and many results point to strong ligand effects on activity and product selectivity. [25] For these reasons, we chose this reaction as a case study.…”

Separation studies in a continuous flow fluorous biphasic system

“…Fluorous biphasic catalysis is a generic technology that is applicable to a wide variety of homogeneous catalytic systems [2,[6][7][8][9][10][11][12]. This work is focused on applying the technology on the hydroformylation of higher alkenes, a reaction system of great industrial importance [1,13].…”

“…Various new approaches have been published for the rhodium catalysed hydroformylation of light and heavy alkenes [15][16][17][18][19][20][21][22][23]. Hydroformylation of higher olefins in fluorous biphasic systems using a rhodium modified catalyst has been successfully studied in batch experiments [6,7] but no continuous studies have yet been reported. A reactor for continuous flow Lewis acid catalysed reactions has recently been published [24].…”

“…The phase behaviour and the mass transfer characteristics of the system are essential for the design of the reactor and separator. Approximate first order kinetics with respect to the substrate concentration, observed in batch experiments, [6] was used for the initial design. However, studies of the phase behaviour of the perfluoromethylcyclohexane/octene/nonanal fluorous system have shown that, because of the incomplete miscibility of the product aldehyde with the fluorous solvent even under the reaction conditions the substrate is reversibly transferred between the two phases [25].…”