A Selective C−H Deprotonation Strategy to Access Functionalized Arynes by Using Hypervalent Iodine

Described here is an efficient method to access highly functionalized arynes from unsymmetrical aryl(mesityl)iodonium tosylate salts. The iodonium salts are prepared in a single pot from either commercially available aryl iodides or arylboronic acids. The aryne intermediates are generated by ortho‐C−H deprotonation of aryl(mesityl)iodonium salt with a commercially available amide base and trapped in a cycloaddition reaction with furan in moderate to good yields. Coupling partners for the aryne intermediates beyond furan are also described, including benzyl azide and alicyclic amine nucleophiles. The regio‐ and chemoselectivity of this reaction is discussed and evidence for the spectator aryl ligand of the iodonium salt as a critical control element in selectivity is presented. Strategische Planung: Unsymmetrische Aryl(mesityl)iodoniumsalze als neuartige Arinvorstufen werden in Eintopfreaktionen aus Aryliodiden und Arylboronsäuren erzeugt und ermöglichen die Herstellung von komplexen Arin‐Zwischenstufen mit hoher Regio‐ und Chemoselektivität. Die Arine können in Cycloadditionen mit Furanen und Aziden sowie in nukleophilen Additionen mit alicyclischen Aminen umgesetzt werden. Mes=Mesityl.