Year: 2024
Type: article
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.
Institutions: University of Minnesota, University of Minnesota System
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $5,510
Awards: G1345980661, G1405578316, G2129658454, G2707391559, G3309432434, Hexadehydro-Diels-Alder (HDDA) Reaction-Enabled Synthesis of Structurally Elaborate, Polycyclic Aromatic Compounds, G4893380297, G5050677891, Upgrade of a 500 MHz NMR Spectrometer for Applications in Biomedical Research, G5217311855, MRI: Acquisition of a single-crystal diffractometer for the University of Minnesota, G7868125508, G9000002454, G956063283
OpenAlex ID: W4391618166