Fe III ‐Based Eutectic Mixtures as Multi‐task and Reusable Reaction Media for Efficient and Selective Conversion of Alkynes into Carbonyl Compounds

An efficient, simple and general protocol for the selective hydration of terminal alkynes into the corresponding methyl ketones has been developed by using a cheap, easy‐to‐synthesise and sustainable Fe III ‐based eutectic mixture [FeCl 3 ⋅ 6H 2 O/ Gly (3 : 1)] as both promoter and solvent for the hydration reaction, working: i) under mild (45 °C) and bench‐type reaction conditions (air); and ii) in the absence of ligands, co‐catalysts, co‐solvents or toxic, non‐abundant and expensive noble transition metals (Au, Ru, Pd). When the final methyl ketones are solid/insoluble in the eutectic mixture, the hydration reaction takes place in 30 min, and the obtained methyl ketones can be isolated by simply decanting the liquid Fe III ‐ DES , allowing the direct isolation of the desired ketones without VOC solvents. By using this straightforward and simple isolation protocol, we have been able to recycle the Fe III ‐based eutectic mixture system up to eight consecutive times. Furthermore, the Fe III ‐eutectic mixture is able to promote the selective and efficient formal oxidation of internal alkynes into 1,2‐diketones, with the possibility of recycling this system up to three consecutive times. Preliminary investigations into a possible mechanism for the oxidation of the internal alkynes seem to indicate that it proceeds through the formation of the corresponding methyl ketones and α ‐chloroketones.