The importance of copper placement in chiral catalysts supported on heteropolyanions: Lacunary vs external exchanged

Abstract

Lacunary [PCuW11O39]5− species modified with chiral bis(oxazoline) leads to very poor results as catalyst in theenantioselective cyclopropanation, in contrast with the Cu-bis(oxazoline) complex exchanged on the Keggin[PW12O40]3− species. The incomplete neutralization and/or exchange of the Keggin species produces a loss insymmetry that leads to spectra in solid phase (IR and NMR) similar to those obtained for the lacunary species.The symmetry is averaged in solution, but additional characterization methods are necessary to determine thetrue nature of the solid heteropolyanionic species. These results demonstrate that the efficiency of copper-bis(oxazoline) complexes is related to its placement in an external exchange position, whereas the copper includedin the heteropolyanion structure is not active for cyclopropanation reactions.