Photosensitized oxidative addition to gold(i) enables alkynylative cyclization of o-alkylnylphenols with iodoalkynes

Zhonghua Xia, Vincent Corcé, Fen Zhao, Cédric Przybylski, Agathe Espagne, Ludovic Jullien, Thomas Le Saux, Yves Gimbert, Héloïse Dossmann, Virginie Mouriès-Mansuy*, Cyril Ollivier, Louis Fensterbank

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

86 Citations (Scopus)

Abstract

The well-established oxidative addition–reductive elimination pathway is the most followed one in transition metal-catalysed cross-coupling reactions. While readily occurring with a series of transition metals, gold(i) complexes have shown some reluctance to undergo oxidative addition unless special sets of ligands on gold(i), reagents or reaction conditions are used. Here we show that under visible-light irradiation, an iridium photocatalyst triggers—via triplet sensitization—the oxidative addition of an alkynyl iodide onto a vinylgold(i) intermediate to deliver C(sp)2–C(sp) coupling products after reductive elimination. Mechanistic and modelling studies support that an energy-transfer event takes place, rather than a redox pathway. This particular mode of activation in gold homogenous catalysis was applied in several dual catalytic processes. Alkynylbenzofuran derivatives were obtained from o-alkynylphenols and iodoalkynes in the presence of catalytic gold(i) and iridium(iii) complexes under blue light-emitting diode irradiation.

Original languageEnglish
Pages (from-to)797-805
Number of pages9
JournalNature Chemistry
Volume11
Issue number9
DOIs
Publication statusPublished - 1 Sept 2019
Externally publishedYes

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