化学
还原消去
光化学
催化作用
铱
氧化加成
氧化磷酸化
试剂
催化循环
甲烷氧化偶联
组合化学
偶联反应
有机化学
生物化学
作者
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
出处
期刊:Nature Chemistry
[Springer Nature]
日期:2019-08-05
卷期号:11 (9): 797-805
被引量:97
标识
DOI:10.1038/s41557-019-0295-9
摘要
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. Studies into gold-catalysed cross-coupling reactions have expanded over recent decades; however, oxidative addition to gold(i) complexes remains challenging. Now it has been shown that a dual catalytic transformation involving iridium photosensitization to trigger oxidative addition to organogold intermediates enables C(sp2)–C(sp) cross-coupling reactions that are useful for the alkynylation of benzofurans.
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