Connecting organic redox-active building blocks through mild noncatalytic C−H activation

• Verfasst von: Wild, Ute [VerfasserIn]
• Verfasst von: Hübner, Olaf [VerfasserIn]
• Verfasst von: Enders, Markus [VerfasserIn]
• Verfasst von: Kaifer, Elisabeth [VerfasserIn]
• Verfasst von: Himmel, Hans-Jörg [VerfasserIn]
• Titel: Connecting organic redox-active building blocks through mild noncatalytic C−H activation
• Verf.angabe: Ute Wild, Olaf Hübner, Markus Enders, Elisabeth Kaifer, and Hans-Jörg Himmel
• E-Jahr: 2022
• Jahr: 01 April 2022
• Umfang: 18 S.
• Fussnoten: Gesehen am 07.06.2022
• Titel Quelle: Enthalten in: European journal of organic chemistry
• Ort Quelle: Weinheim : Wiley-VCH Verl., 1998
• Jahr Quelle: 2022
• Band/Heft Quelle: (2022), 15, Artikel-ID e202200349, Seite 1-18
• ISSN Quelle: 1099-0690
• DOI: doi:10.1002/ejoc.202200349
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: C−H activation
• Sach-SW: Electronic coupling
• Sach-SW: Guanidines
• Sach-SW: Oxidation
• Sach-SW: Redox chemistry
• K10plus-PPN: 180613604X
• K10plus-PPN:
  Universitätsbibliothek
• Lokale URL UB: Zum Volltext

Abstract

Compounds with two or more redox-active units, connected by a bridge that supports electronic coupling between the units, have been studied for a long time. Redox reactions could result in mixed-valence compounds, in which the electronic structure depends on the degree of electronic coupling. Here we report the synthesis of the first molecule in which two redox-active guanidines are connected through a bridge. The compound is synthesized in an unprecedented, simple one-step procedure involving an atom-economically favorable, non-catalytic C−H activation reaction at room temperature from novel 1,2,4-trisguanidino-benzene molecules and 1,4-benzenedithiol. We then apply similar protocols to introduce other substituents in 5-position of a 1,2,4-trisguanidino-benzene molecule, demonstrating the scope of these exceptional C−H activation reactions. Finally, we report the synthesis of a hexakisguanidino-biphenyl by direct coupling of two trisguanidino-benzene units through C−H activation. Its oxidation leads to the first mixed-valence compound with charge delocalization between two redox-active guanidino units. The redox states of the resulting novel compounds are systematically studied.