Phosphorane‐Promoted C−C Coupling during Aryne Annulations

Abstract: Arynes are fleeting, high‐energy intermediates that undergo myriad trapping reactions by nucleophiles. Their unusual reactivity compared to other electrophiles can spur unexpected mechanistic pathways enroute to the formation of benzenoid products. Herein we explore a particularly unique case of thermally generated arynes reacting with phosphoranes to form helical dibenzothiophenes and ‐selenophenes. Multiple new helical polycyclic aromatic products are reported. DP4+ and X‐ray crystallographic analysis were used in tandem to confirm the structural topologies of selected products and to demonstrate the utility of DP4+ for distinguishing between isomeric polycyclic aromatic compounds. Lastly, we discuss a plausible mechanism consistent with DFT computations that accounts for the product formation; namely, ligand coupling (i.e., reductive elimination) within a hypervalent, pentacarbon‐ligated σ‐phosphorane furnishes the dibenzothio‐ or dibenzoselenophene.

Object Details

• Location: Deutsche Nationalbibliothek Frankfurt am Main
• Extent: Online-Ressource
• Language: Englisch

References and Relationships

• Bibliographic citation: Phosphorane‐Promoted C−C Coupling during Aryne Annulations ; day:05 ; month:03 ; year:2024 ; extent:7 ; Angewandte Chemie / International edition. International edition ; (05.03.2024) (gesamt 7)

Contributors, Places and Time

• Creator: Kevorkian, Paul V. ; Sneddon, Dorian S. ; Ritts, Casey B. ; Hoye, Thomas R.

Further information

• DOI: 10.1002/anie.202318774
• URN: urn:nbn:de:101:1-2024030614183423023161
• Rights: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
• Last update: 14.08.2025, 10:56 AM CEST