Reactant-induced photoactivation of in situ generated organogold intermediates leading to alkynylated indoles via Csp2-Csp cross-coupling - ENS - École normale supérieure Accéder directement au contenu
Article Dans Une Revue Nature Communications Année : 2022

Reactant-induced photoactivation of in situ generated organogold intermediates leading to alkynylated indoles via Csp2-Csp cross-coupling

Jérémy Forté
Thomas Le Saux
Cyril Ollivier

Résumé

Abstract Photosensitization of organogold intermediates is an emerging field in catalysis. In this context, an access to 2,3-disubstituted indoles from o -alkynyl aniline and iodoalkyne derivatives via a gold-catalyzed sequence under visible-light irradiation and in the absence of an exogenous photocatalyst was uncovered. A wide scope of the process is observed. Of note, 2-iodo-ynamides can be used as electrophiles in this cross-coupling reaction. The resulting N -alkynyl indoles lend themselves to post-functionalization affording valuable scaffolds, notably benzo[a]carbazoles. Mechanistic studies converge on the fact that a potassium sulfonyl amide generates emissive aggregates in the reaction medium. Static quenching of these aggregates by a vinylgold(I) intermediate yields to an excited state of the latter, which can react with an electrophile via oxidative addition and reductive elimination to forge the key C-C bond. This reactant-induced photoactivation of an organogold intermediate opens rich perspectives in the field of cross-coupling reactions.
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hal-03813241 , version 1 (13-10-2022)

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Fen Zhao, Mehdi Abdellaoui, Wided Hagui, Maria Ballarin-Marion, Jérôme Berthet, et al.. Reactant-induced photoactivation of in situ generated organogold intermediates leading to alkynylated indoles via Csp2-Csp cross-coupling. Nature Communications, 2022, 13 (1), pp.2295. ⟨10.1038/s41467-022-29982-2⟩. ⟨hal-03813241⟩
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