Photochemical reductive C-C coupling with a guanidine electron donor

• Verfasst von: Wiesner, Sven [VerfasserIn]
• Verfasst von: Walter, Petra [VerfasserIn]
• Verfasst von: Wagner, Arne [VerfasserIn]
• Verfasst von: Kaifer, Elisabeth [VerfasserIn]
• Verfasst von: Himmel, Hans-Jörg [VerfasserIn]
• Titel: Photochemical reductive C-C coupling with a guanidine electron donor
• Verf.angabe: Sven Wiesner, Petra Walter, Arne Wagner, Elisabeth Kaifer, and Hans-Jörg Himmel
• E-Jahr: 2016
• Jahr: 27 September 2016
• Umfang: 10 S.
• Fussnoten: Gesehen am 12.08.2020
• Titel Quelle: Enthalten in: European journal of organic chemistry
• Ort Quelle: Weinheim : Wiley-VCH Verl., 1998
• Jahr Quelle: 2016
• Band/Heft Quelle: (2016), 29, Seite 5045-5054
• ISSN Quelle: 1099-0690
• DOI: doi:10.1002/ejoc.201600978
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: C-C coupling
• Sach-SW: Photochemistry
• Sach-SW: Radicals
• Sach-SW: Reaction mechanisms
• Sach-SW: Redox reactions
• K10plus-PPN: 1726850048

Abstract

The metal‐free photoinduced reductive C–C coupling reactions of a number of substituted benzyl halides (15 examples) with the organic electron‐donor 2,3,5,6‐tetrakis(tetramethylguanidino)pyridine are evaluated. Depending on the substituents at the benzyl group, a C–C coupling product yield in the range 50–95 % is achieved. The photochemical benzyl‐radical formation by homolytic N–C bond cleavage of the initially formed benzyl‐pyridinium salts is the rate‐determining step of these reactions. Electron‐withdrawing as well as ‐donating substituents at the phenyl group increase the reaction rate. Quantum chemical computations did not reveal any correlation between either the enthalpy or Gibbs free energy of the N–C bond cleavage step and the experimentally determined first‐order rate constants. Instead, the structural difference between the excited state generated by irradiation and the electronic ground state of the pyridinium ions could be used to rationalize the differences in the reaction rates.