Light‐Induced Mechanistic Divergence in Gold(I) Catalysis: Revisiting the Reactivity of Diazonium Salts. (11th October 2019)

• Record Type: Journal Article
• Authors: Taschinski, Svenja; Döpp, René; Ackermann, Martin; Rominger, Frank; de Vries, Folkert; Menger, Maximilian F. S. J.; Rudolph, Matthias; Hashmi, A. Stephen K.; Klein, Johannes E. M. N.
• Is Part Of: Angewandte Chemie. Volume 131:Number 47(2019)
• Page Start: 17144
• Page End: 17149
• Publication Date: 2019-10-11
• Subjects: Diazoverbindungen -- Homogene Goldkatalyse -- Mechanistische Divergenz -- Photochemie -- Vinylgold-Intermediat; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201908268
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: In a systematic study of the Au‐catalyzed reaction of o ‐alkynylphenols with aryldiazonium salts, we find that essentially the same reaction conditions lead to a change in mechanism when a light source is applied. If the reaction is carried out at room temperature using a Au I catalyst, the diazonium salt undergoes electrophilic deauration of a vinyl Au I intermediate and provides access to substituted azobenzofurans. If the reaction mixture is irradiated with blue LED light, C−C bond formation due to N2 ‐extrusion from the diazonium salt is realized selectively, using the same starting materials without the need for an additional photo(redox) catalyst under aerobic conditions. We report a series of experiments demonstrating that the same vinyl Au I intermediate is capable of producing the observed products under photolytic and thermal conditions. The finding that a vinyl Au I complex can directly, without the need for an additional photo(redox) catalyst, result in C−C bond formation under photolytic conditions is contrary to the proposed mechanistic pathways suggested in the literature till date and highlights that the role of oxidation state changes in photoredox catalysis involving Au is thus far only poorly understood and may hold surprises for the future. Computational results indicate that photochemical activation can occur directly from a donor–acceptor complex formed between the vinyl Au I intermediate and the diazonium salt. Abstract : Die Au‐katalysierte Reaktion von o ‐Alkinylphenolen mit Aryldiazoniumsalzen erfährt beim Einsatz einer Lichtquelle eine Änderung des Mechanismus. Wird die Reaktion bei Raumtemperatur mit einem Au I ‐Katalysator durchgeführt, unterliegt das Diazoniumsalz einer elektrophilen Deaurierung eines Vinyl‐Au I ‐Intermediats unter Bildung substituierter Azobenzofurane. Wird das Reaktionsgemisch mit blauem LED‐Licht bestrahlt, ist eine C‐C‐Bindungsbildung durch N2 ‐Extrusion aus dem Diazoniumsalz zu beobachten.