Iron-Catalyzed Cross-Coupling of Thioesters and Organomanganese Reagents

We report a Fukuyama-type coupling of thioesters with aliphatic organomanganese reagents utilizing a cheap and easily available iron(III) catalyst. The reactions exhibit a wide tolerance of solvents and functional groups (e.g. ketones, esters, aryl(pseudo)halides) allowing for the conversion of thioesters derived from natural products and pharmaceutical compounds. Investigations showed a strong steric influence from each reaction component (carboxylic moiety, thiol substituent and manganese reagent), which enabled regioselective transformation of dithioesters. Tandem transformations combining the coupling with an additional step were observed. Our experiments provide insights into the potential of the employed aliphatic manganese reagents, such as the interaction between iron, manganese and oxygen, which allows for a smooth conversion.