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

ABSTRACT: Reactions of ?,?-unsaturated aromatic thioketones 1 (thiochalcones) with Fe3 (CO)12 leading to ?4 -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.

SUBMITTER: Buday P 

PROVIDER: S-EPMC7540601 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

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

Buday Philipp P   Seeber Phillip P   Zens Clara C   Abul-Futouh Hassan H   Görls Helmar H   Gräfe Stefanie S   Matczak Piotr P   Matczak Piotr P   Kupfer Stephan S   Weigand Wolfgang W   Mloston Grzegorz G  

Chemistry (Weinheim an der Bergstrasse, Germany) 20200810 50

Reactions of α,β-unsaturated aromatic thioketones 1 (thiochalcones) with Fe<sub>3</sub> (CO)<sub>12</sub> leading to η<sup>4</sup> -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  ...[more]

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