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Updated: Jan 19, 2026
![Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F60786.jpg&w=3840&q=50)
Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
Published on: July 17, 2020
Redox-Active Guanidines in Proton-Coupled Electron-Transfer Reactions: Real Alternatives to Benzoquinones?
Ute Wild1, Olaf Hübner1, Hans-Jörg Himmel1
1Anorganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Abstract:
Guanidino-functionalized aromatics (GFAs) are readily available, stable organic redox-active compounds. In this work we apply one particular GFA compound, 1,2,4,5-tetrakis(tetramethylguanidino)benzene, in its oxidized form in a variety of oxidation/oxidative coupling reactions to demonstrate the scope of its proton-coupled electron transfer (PCET) reactivity. Addition of an excess of acid boosts its oxidation power, enabling the oxidative coupling of substrates with redox potentials of at least +0.77 V vs. Fc+ /Fc. The green recyclability by catalytic re-oxidation with dioxygen is also shown. Finally, a direct comparison indicates that GFAs are real alternatives to toxic halo- or cyano-substituted benzoquinones.
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