Abstract
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.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
