“Catalysis in a Tea Bag”: Synthesis, Catalytic Performance and Recycling of Dendrimer-Immobilised Bis- and Trisoxazoline Copper Catalysts

Graphical Abstract

Trapped in a “tea bag”: Membrane bags, fabricated from a dialysis membrane, have been employed as semipermeable containers for dendrimer-immobilised oxazoline–copper(II) Lewis acid catalysts. Dipping them into reactant solutions leads to the catalytic conversion of the substrates, which penetrate the membrane as does the product in the reverse direction (see scheme).

Abstract

Trapped in a “tea bag”: Membrane bags, fabricated from a dialysis membrane, have been employed as semipermeable containers for dendrimer-immobilised oxazoline–copper(II) Lewis acid catalysts. Dipping them into reactant solutions leads to the catalytic conversion of the substrates, which penetrate the membrane as does the product in the reverse direction (see scheme).

Bis- and trisoxazolines (BOX and trisox), containing a linker unit in the ligand backbone that allows their covalent attachment to carbosilane dendrimers, have been employed as polyfunctional ligands for recyclable Cu^II Lewis acid catalysts that were immobilised in a membrane bag. The oxazolines contained an alkynyl unit attached to their backbone that was deprotonated with LDA or BuLi and then reacted with the chlorosilyl termini of zeroth-, first- and second-generation carbosilane dendrimers in the presence of TlPF₆. The functionalised dendritic systems were subsequently separated from excess ligand by way of dialysis. The general catalytic potential of these systems was assessed by studying two benchmark reactions, the α-hydrazination of a β-keto ester as well as the Henry reaction of 2-nitrobenzaldehyde with nitromethane. For both reactions the bisoxazoline-based catalysts displayed superior selectivity and, in particular, catalyst activity. The latter was interpreted as being due to the hindered decoordination of the third oxazoline unit, the key step in the generation of the active catalyst, in the immobilised trisox–copper complexes. Solutions of the second-generation dendrimer catalysts were placed in membrane bags, fabricated from commercially available dialysis membranes, with the purpose of catalyst recycling based on dialysis. Overall, the supported BOX catalyst gave good and highly reproducible results throughout the study, whereas the performance of the trisox dendrimer system decreased monotonically. The reason for the different behaviour is the markedly lower activity of trisox-based catalysts relative to those based on the BOX ligand. This necessitated an increased reaction time for each cycle of the trisox derivatives, resulting in higher levels of catalyst leaching, which was attributed to a modification of the structure of the membrane by its exposure to the solvent trifluoroethanol at 40 °C.