Dehydrogenative Coupling Reactions with Oxidized Guanidino‐Functionalized Aromatic Compounds: Novel Options for σ‐Bond Activation. Issue 34 (19th July 2016)

• Record Type: Journal Article
• Authors: Wild, Ute; Federle, Stefanie; Wagner, Arne; Kaifer, Elisabeth; Himmel, Hans‐Jörg
• Is Part Of: Chemistry. Volume 22:Issue 34(2016)
• Page Start: 11971
• Page End: 11976
• Publication Date: 2016-07-19
• Subjects: bond activation -- coupling reactions -- guanidine -- redox chemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201602236
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: We present a new option for metal‐free σ‐bond activation, making use of oxidized, guanidino‐functionalized aromatic compounds (GFAs). We demonstrate this new option by the homocoupling reactions of thiols and phosphines. The kinetics and the reaction pathway were studied by a number of experiments (including heterocoupling of thiols and phosphines), supported by quantum‐chemical computations. Reaction of the oxidized GFA with p ‐dihydrobenzoquinone to give p ‐benzoquinone shows that typical proton‐coupled electron‐transfer reactions are also possible. Abstract : Metal‐free activation : Due to the combination of a high proton affinity and a favorable and tunable redox potential, guanidino‐functionalized aromatic compounds (GFAs) are ideal reagents for proton‐coupled electron‐transfer reactions. The focus of this work is the dehydrogenative coupling of thiols and phosphines with an oxidized GFA (see figure).