Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, C/ Marcel⋅lí Domingo s/n, 43007, Tarragona, Spain.
Chemistry. 2021 Aug 16;27(46):11989-11996. doi: 10.1002/chem.202101751. Epub 2021 Jun 28.
A library of gold(I) chloride complexes with phosphine ligands incorporating pendant (thio)urea and squaramide H-bond donors was prepared with the aim of promoting chloride abstraction from Au(I) via H-bonding. In the absence of silver additives, complexes bearing squaramides and trifluoromethylated aromatic ureas displayed good catalytic activity in the cyclization of N-propargyl benzamides, as well as in a 1,6-enyne cycloisomerization, a tandem cyclization-indole addition reaction and the hydrohydrazination of phenylacetylene. Kinetic studies and DFT calculations indicate that the energetic span of the reaction is accounted by both the chloride abstraction step, facilitated by the bidentate H-bond donor via an associative mechanism, and the subsequent cyclization step.
一个包含磷配体的金（I）氯化物配合物库，其中包含悬垂的（硫）脲和双缩胍氢键供体，旨在通过氢键促进从 Au（I）中提取氯化物。在没有银添加剂的情况下，带有双缩胍和三氟甲基取代芳香脲的配合物在 N-炔丙基苯甲酰胺的环化、1,6-烯炔环异构化、串联环化-吲哚加成反应和苯乙炔的水合肼化反应中表现出良好的催化活性。动力学研究和 DFT 计算表明，反应的能量跨度由通过缔合机制通过双齿氢键供体促进的氯化物提取步骤和随后的环化步骤共同决定。
