Iron(0)-Mediated Stereoselective (3+2)-Cycloaddition of Thiochalcones via a Diradical Intermediate

Reactions of α,β-unsaturated aromatic thioketones 1 (thiochalcones) with Fe₃ (CO)₁₂ leading to η⁴ -1-thia-1,3-diene iron tricarbonyl complexes 2, [FeFe] hydrogenase mimics 3, and the thiopyrane adduct 4 are described. Obtained products have been characterized by X-ray crystallography and by computational methods. Completely regio- and diastereoselective formation of the five-membered ring system in products 3, containing four stereogenic centers, can be explained by an unprecedented, stepwise (3+2)-cycloaddition of two thiochalcone molecules mediated by Fe₃ (CO)₁₂ . Quantum chemical calculations aimed at elucidation of the reaction mechanism, suggest that the formal (3+2)-cycloaddition proceeds via sequential intramolecular radical transfer events upon homolytic cleavage of one carbon-sulfur bond leading to a diradical intermediate.