Au(I) catalysts promote the intramolecular cycloisomerization of 1,n-enynes, as well as facilitate reactions with alcohols, characteristics that have led to their wide-spread in the synthesis of complex natural products. Literature reports of Cu and Ag species catalyzing the same or similar reactions are much less common. Here, we utilize molecular volcano plots to assess the activity of 45 coinage metal phosphine/phosphite catalysts possessing a variety of stereoelectronic properties for the methoxycyclization reaction of a prototypical 1,5-enyne. Our analysis reveals that the intrinsic properties of gold allow it to be coupled with a wide range of ligands, all of which exhibit high catalytic activity. On the other hand, the coupling of silver and copper with more traditional phosphines, such as triphenylphosphine, leads to catalysts with diminished catalytic ability. The activity of Ag and Cu species, however, can be enhanced by appending ligands with strong π-accepting character, which shifts these species closer to the volcano peak.

中文翻译：

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铸币金属催化剂对 1,5-烯炔的甲氧基环化：黄金总是优越吗？

Au(I) 催化剂促进 1, n的分子内环异构化-enynes，以及促进与醇的反应，这些特性导致它们在复杂天然产物的合成中得到广泛应用。关于催化相同或相似反应的 Cu 和 Ag 物种的文献报道要少得多。在这里，我们利用分子火山图来评估 45 种铸币金属膦/亚磷酸酯催化剂的活性，这些催化剂具有各种立体电子特性，用于原型 1,5-烯炔的甲氧基环化反应。我们的分析表明，金的固有特性使其能够与多种配体偶联，所有这些配体都表现出高催化活性。另一方面，银和铜与更传统的膦（如三苯基膦）的偶联导致催化剂催化能力减弱。然而，Ag 和 Cu 物种的活性，