Hydration of aromatic terminal alkynes catalyzed by iron(III) sulfate hydrate under chlorine-free conditions

The hydration of aromatic terminal alkynes performed in acetic acid in the presence of catalytic hydrate ironIII sulfate, Fe2(SO 4)3·nH2O (4-9 mol %), yields the derived aryl methyl ketones with good to excellent yields. Under comparable conditions (18 mol %, 95 C, 24 h), bifunctional substrates were transformed into the monoacetyl or the diacetyl derivatives, depending on the structure of the aromatic diyne. The reaction is compatible with aryl substituents of different nature and ring positions, including hydroxyl, carbonyl groups, and cumulated hydrocarbons. The soft character of the non nucleophilic sulfate anion allows for activation of the triple bond toward carbonoxygen bond formation in the Brønsted acidic medium. The proposed protocol is based on readily available and non toxic materials, in the absence of chlorine atoms in either the solvent or the metal catalyst.