Lalonde Rebecca L, Brenzovich William E, Benitez Diego, Tkatchouk Ekaterina, Kelley Kotaro, Goddard William A, Toste F Dean
Department of Chemistry, University of California Berkeley, Berkeley, CA, USA. ; Tel: +1 510-642-2850.
Materials and Process Simulation Center, California Institute of Technology, Pasadena, CA, USA.
Chem Sci. 2010 Aug 1;1(2). doi: 10.1039/C0SC00255K.
Alkylgold(I) complexes were formed from the gold(I)-promoted intramolecular addition of various amine nucleophiles to alkenes. These experiments provide the first direct experimental evidence for the elementary step of gold-promoted nucleophilic addition to an alkene. Deuterium-labeling studies and X-ray crystal structures provide support for a mechanism involving -addition of the nucleophile to a gold-activated alkene, which is verified by DFT analysis of the mechanism. Ligand studies indicate that the rate of aminoauration can be drastically increased by use of electron-poor arylphosphines, which are also shown to be favored in ligand exchange experiments. Attempts at protodeauration lead only to recovery of the starting olefins, though the gold can be removed under reducing conditions to provide the purported hydroamination products.
烷基金（I）配合物是由金（I）促进的各种胺亲核试剂与烯烃的分子内加成反应形成的。这些实验为金促进的亲核试剂加成到烯烃的基本步骤提供了首个直接实验证据。氘标记研究和X射线晶体结构为涉及亲核试剂向金活化烯烃进行 -加成的机理提供了支持，该机理通过对其进行密度泛函理论（DFT）分析得到验证。配体研究表明，使用贫电子芳基膦可大幅提高氨金化反应速率，且在配体交换实验中也显示出这种膦更受青睐。尽管在还原条件下金可以被除去以得到所谓的氢胺化产物，但进行脱金质子化的尝试仅导致起始烯烃的回收。
