Immobilisation of the BINAP Ligand on Dendrimers and Hyperbranched Polymers: Dependence of the Catalytic Properties on the Linker Unit

A series of immobilised Carbo‐BINAP ligands has been synthesised using poly(propylene imine) (PPI) dendrimers as soluble supports. They contain up to 64 BINAP ligands at their periphery without an additional linking unit. Despite the high steric requirements of the ligand, all dendrimers could be completely functionalised, resulting in the immobilised systems in good yields. Furthermore, the immobilisation strategy that worked out for the fixation of AMINAP ligands with additional linking units as well as of Carbo‐BINAP ligands without additional linking units on dendrimers has thus been extended to less regularly hyperbranched poly(ethylene imines) (PEI) as soluble supports. In that way it has been possible to attach on average 9, 26, and 138 Glutaroyl‐AMINAP or Carbo‐BINAP ligands to PEIs of different molecular weights. The catalytic properties of these systems in the copper‐catalysed hydrosilylation of acetophenone were investigated. The dendritic PPI‐bound Carbo‐BINAP ligands displayed a strong dependence of enantioselectivity and activity on the generation of the dendrimer. For the Carbo‐BINAP and Glutaroyl‐AMINAP ligands immobilised on the hyperbranched polymers, however, activities and enantioselectivities comparable to those of the mononuclear catalysts were found. The macromolecular, immobilised BINAP ligands could be recycled several times without any observable loss of activity or enantioselectivity.