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

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. Dual photo- and metal-catalysis is generally not well-understood when the metal catalyst is a gold complex. Here the authors show that a variation of a known metallaphotoredox annulation is possible without an added photocatalyst, proceeding putatively through a gold-intermediate photosensitization by the aggregate of a potassium amide reactant, and yielding indole derivatives.

Automated summary

Photosensitization of organogold intermediates is an emerging field in catalysis. Researchers have discovered a gold-catalyzed reaction that produces 2,3-disubstituted indoles from specific substrates using visible-light irradiation without the need for an external photocatalyst. The reaction has a wide range of applications and involves the formation of emissive aggregates through the interaction of a potassium sulfonyl amide reactant, leading to photoactivation of the organogold intermediate.