A smart palladiumcatalyst in ionic liquid for tandem processes

Abstract

New catalytic systems based on in situ and preformed palladium nanoparticles in ionic liquids (characterised by TEM) starting from palladium acetate or dipalladiumtris(dibenzylideneacetone) have been applied in the synthesis of 4-phenylbutan-2-one (II), a model compound for the preparation of fragrances. Imidazolium-based ionic liquid containing a methyl hydrogenophosphonate anion leads to an efficient Pd-catalyzed tandem coupling/reduction process, taking advantage of the multi-role of this solvent (nanoparticles stabiliser, base, hydrogen transfer agent). The influence of the mono-phosphine ligands (1–3) on the catalyst has been evaluated, showing that the ligand-free palladium system turns into the most appropriate for the formation of II using Pd(OAc)₂ as precursor. Fine-tuning conditions involved in this multi-parameter process have led us to propose a plausible mechanism based on the hydrogen transfer coming from the methyl hydrogenophosphonate anion.