The Rh-catalyzed aqueous biphasic hydroformylation with the bidentate ligand SulfoXantPhos was investigated for different phase transfer agents (PTA). As such, polymer latices and microemulsions formed by non-ionic surfactants were used. In general, a higher PTA concentration enhances the reaction progress. The feasibility of catalyst recycling by simple phase separation is shown in principle.The Rh losses are low in the surfactant system and promising for a technical approach.

The kinetics of the catalytic hydrogenation of dimethyl itaconate (DMI) was studied in a biphasic cyclohexane-water system and in a [Triton X-100/1-pentanol]/cyclohexane/water microemulsion, in both cases using the water-soluble catalyst complex Rh-TPPTS. The reaction was carried out at a pressure of 1.1 bar and in the temperature range 298-308 K. A typical profile of a zero-order reaction was observed in the case of the biphasic system. Against that the reaction order for DMI changed to 1 in a microemulsion. A rate law based on an Osborn-Wilkinson-like kinetics was used to describe the experimental results which were governed by the irreversible attack of free DMI at the rhodium complex. The activation energy of the ratedetermining step is 53 kJ mol -1 and is similar in both systems.

The reaction medium in the Suzuki coupling shown is a three‐phase surfactant system. This medium offers advantages over conventional solvents in the reaction conversion and also in catalyst recovery. The reuse of the catalyst substantially increases the overall turnover number of the catalyst, a desirable factor in cost‐effective industrial applications. TPPTS=3,3′,3′′‐phosphanetriyltris(benzenesulfonic acid) trisodium salt.

The potential of surfactant based reaction media was studied with different homogeneous catalytic reactions. Micellar systems with the surfactants (p-tert-octylphenoxy) polyethoxyethanol (Triton X-100) and dodecyl sulfate sodium salt were used as reaction media for the enantioselective catalytic hydrogenation of dimethyl itaconate (DMI) with the Rh catalyst complexed with the chiral ligand (2S,4S)-1-tert-butoxycarbonyl-4diphenylphosphino-2-(diphenylphosphinometyl)-pyrrolidine (BPPM) at 30 °C and 1.1 bar, obtaining an enantiomeric excess (ee) of up to 69%. After complete hydrogenation was achieved, micellar enhanced ultrafiltration (MEUF) was used to recycle the catalyst achieving up to 95% retention. A microemulsion system stabilized with the surfactant Triton X-100 was used as alternative reaction media for the hydrogenation of DMI with a Rh catalyst complexed with the water-soluble tris(3-sulfophenyl)phosphine trisodium salt (TPPTS) at 50 °C and 1.1 bar. With the Triton X-100 system, phase separation by temperature induced separation allowed for up to four repetitive batches of DMI hydrogenations, resulting in a TON of 1530. Suzuki coupling for the synthesis of 4′-methyl-2-biphenylcarbonitrile proceeded faster in a narrow range alkylpolyglycol ether (Novel 8 ) Novel 1216CO-8 Ethoxylate) three-phase system than in an dioctyl sulfosuccinate sodium salt (AOT) two-phase system, demonstrating the retarding effect of the salinization on the reaction rate.