Sulfurane [S(IV)]-Mediated Fusion of Benzynes Leads to Helical Dibenzofurans
Casey B. Ritts, Thomas R. Hoye
Abstract
Here we disclose a sulfurane-mediated method for the formation of dimeric dibenzofuran helicenes via the reaction between diaryl sulfoxides and hexadehydro-Diels-Alder (HDDA) derived benzynes. A variety of S-shaped and U-shaped helicenes were formed under thermal conditions. Both experimental and DFT studies support a sulfur(IV)-based coupling (aka ligand coupling) mechanism involving tetracarbo-ligated S(IV) intermediates undergoing reductive elimination to afford the helicene products. This process involves the de novo generation of five new rings in a single operation and constitutes a new method for the construction of topologically interesting, polycyclic aromatic compounds.
Topics & Concepts
ChemistryAryneHeliceneDibenzofuranLigand (biochemistry)Combinatorial chemistryReductive eliminationComputational chemistryStereochemistryMoleculeMedicinal chemistryOrganic chemistryCatalysisReceptorBiochemistryCyclization and Aryne ChemistrySynthesis and Properties of Aromatic CompoundsSynthesis and pharmacology of benzodiazepine derivatives