Reiersølmoen Ann Christin, Battaglia Stefano, Orthaber Andreas, Lindh Roland, Erdélyi Máté, Fiksdahl Anne
Department of Chemistry, Norwegian University of Science and Technology, Høgskoleringen 5, 7491 Trondheim, Norway.
Department of Chemistry-BMC Uppsala University, Husargatan 3, 75237 Uppsala, Sweden.
Inorg Chem. 2021 Mar 1;60(5):2847-2855. doi: 10.1021/acs.inorgchem.0c02720. Epub 2020 Nov 10.
Gold(III) complexes are versatile catalysts offering a growing number of new synthetic transformations. Our current understanding of the mechanism of homogeneous gold(III) catalysis is, however, limited, with that of phosphorus-containing complexes being hitherto underexplored. The ease of phosphorus oxidation by gold(III) has so far hindered the use of phosphorus ligands in the context of gold(III) catalysis. We present a method for the generation of ,-chelated gold(III) complexes that circumvents ligand oxidation and offers full counterion control, avoiding the unwanted formation of AuCl. On the basis of NMR spectroscopic, X-ray crystallographic, and density functional theory analyses, we assess the mechanism of formation of the active catalyst and of gold(III)-mediated styrene cyclopropanation with propargyl ester and intramolecular alkoxycyclization of 1,6-enyne. ,-chelated gold(III) complexes are demonstrated to be straightforward to generate and be catalytically active in synthetically useful transformations of complex molecules.
金（III）配合物是多功能催化剂，可实现越来越多的新型合成转化。然而，我们目前对均相金（III）催化机理的理解有限，含磷配合物的催化机理迄今尚未得到充分探索。到目前为止，金（III）对磷的氧化作用阻碍了磷配体在金（III）催化中的应用。我们提出了一种生成η-螯合金（III）配合物的方法，该方法可避免配体氧化并实现完全的抗衡离子控制，避免了不需要的AuCl的形成。基于核磁共振光谱、X射线晶体学和密度泛函理论分析，我们评估了活性催化剂的形成机理以及金（III）介导的苯乙烯与炔丙基酯的环丙烷化反应和1,6-烯炔的分子内烷氧基环化反应。结果表明，η-螯合金（III）配合物易于生成，并且在复杂分子的合成有用转化中具有催化活性。
