Transition Metal Catalysts Solubilized in Micellar Aggregates

Transition Metal Catalysts Solubilized In Micellar Aggregates 

The chiral ligand was in all cases (2S,4S)-N-tert-butoxycarbonyl-4-diphenylphos-phino-2-diphenylphosphinomethylpyrrolidine (BPPM) and the catalyst was formed in an in situ system of [Rh(COD)2] BFT The asymmetric hydrogenation is well investigated in organic solvents like methanol, but the presence of water usually causes loss of activity and enantioselectivity because of the low solubility of both the catalyst and the substrate in water [27, 29]. The addition of low-molecular surfactants or commercially available polymeric amphiphiles increases the activity (here given as time of consumption of half the stoichiometric volume of hydrogen, t/2) as well as the enantioselectivity [4]. Tab. 6.1 summarizes selected experiments with different polymeric amphiphiles. 

It turned out that for all the polymeric amphiphiles of the (EO) -(PO)m-(EO) type there was an increase in enantioselectivity compared with the reaction without amphiphile. Moreover, the ratio of the length of the (PO) block compared with the (EO) block seemed to determine enantioselectivity and activity and not the cmc (critical micelle concentration). A (PO) block length of 56 units works best with different length of the (EO)n block in this type of hydrogenation [30]. for the work-up of the experiments, G. Oehme et al. used the extraction method, but initial experiments failed and the catalyst could not be recycled that way. To solve this problem the authors applied a membrane reactor in combination with the amphiphile (EO)37-(PO)5g-(EO)37 (Tab. 6.1, entry 9) [31]. By doing so, the poly-mer/Rh-catalyst was retained and could be reused several times without loss of activity and enantioselectivity by more than 99%. 

Two approaches have been studied in the past to avoid metal leaching, either by metal colloids stabilized in miceUar core or catalyst bound to the micellar structures and will therefore discussed in the following sections. 

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