AMINOINDANES IN OXYGEN TRANSFER REACTIONS, 2 - COPPER-COMPLEXES AS FUNCTIONAL MODELS FOR DOPAMINE-BETA-HYDROXYLASE STEREOSPECIFIC OXYGEN-ATOM TRANSFER

The stereochemistry of oxygen atom transfer mediated by copper-oxygen species has been studied through a substrate binding ligand approach. Copper(II) [(IndPY2)Cu](CF3SO3)(2) (2a) and copper(I) [(IndPY2)Cu]PF6 (5a) complexes were prepared and exposed to O-2 in media of benzoin/NE t3/CH2Cl2 and CH2Cl2, respectively. In both cases, highly regio- and s tereoselective oxygen atom transfer to the benzylicC-H bond of the ind ane ligand occurred. Using deuterium-labelled copper complexes 2b and 5b, we found that, in both cases, the oxygen atom transfer occurs with retention of configuration. The high deuterium kinetic isotope effect s (7.6 and 11, respectively), determined by C-13-NMR spectroscopy, str ongly suggest the intermediacy of two different copper-oxygen reactive species.