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Title: 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.  more » « less
Award ID(s):
2155042
PAR ID:
10504913
Author(s) / Creator(s):
; ; ;
Publisher / Repository:
Wiley
Date Published:
Journal Name:
Angewandte Chemie International Edition
Volume:
63
Issue:
14
ISSN:
1433-7851
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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