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Paramagnetic Palladacycles with PdIII Centers Are Highly Active Catalysts for Asymmetric Aza-Claisen Rearrangements

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journal contribution
posted on 14.03.2012, 00:00 by Simon H. Eitel, Matthias Bauer, David Schweinfurth, Naina Deibel, Biprajit Sarkar, Harald Kelm, Hans-Jörg Krüger, Wolfgang Frey, René Peters
A combination of spectroscopic and electrochemical methodsXANES, EXAFS, X-ray, 1H NMR, EPR, Mössbauer, and cyclic voltammetrydemonstrate that the most efficient Pd catalysts for the asymmetric rearrangement of allylic trifluoroacetimidates unexpectedly possess in the activated oxidized form a PdIII center bound to a ferrocene core which remains unchanged (FeII) during the oxidative activation. These are the first recognized PdIII complexes acting as enantioselective catalysts.