关于通过金（I）/金（III）催化实现配体促进的烯烃氧芳基化/乙烯基化反应的机理见解
Mechanistic Insights about the Ligand-Enabled Oxy-arylation/vinylation of Alkenes via Au(I)/Au(III) Catalysis.
作者信息
Rigoulet Mathilde, Miqueu Karinne, Bourissou Didier
机构信息
CNRS/Université Paul Sabatier, UPS Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA UMR 5069), 118 route de Narbonne, 31062, Toulouse, France.
CNRS/Université de Pau et des Pays de l'Adour, E2S-UPPA, Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Matériaux (IPREM UMR 5254), Hélioparc, 2 Avenue du Président Angot, 64053, Pau Cedex 09, France.
出版信息
Chemistry. 2022 Oct 26;28(60):e202202110. doi: 10.1002/chem.202202110. Epub 2022 Aug 25.
The mechanism of oxy-arylation/vinylation of alkenes catalyzed by the (MeDalphos)AuCl complex was comprehensively investigated by DFT. (P,N)Au(Ph) and (P,N)Au(vinyl) are key intermediates accounting for the activation of the alkenols and for their cyclization by outer-sphere nucleophilic attack of oxygen. The 5-exo and 6-endo paths have been computed and compared, reproducing the peculiar regioselectivity difference observed experimentally between 4-penten-1-ol, (E) and (Z)-4-hexen-1-ols. Examining the way the alkenol coordinates to gold (more η or η ) can offer, in some cases, a simple way to predict the favored path of cyclization.
通过密度泛函理论（DFT）全面研究了(MeDalphos)AuCl配合物催化的烯烃氧芳基化/乙烯基化反应机理。(P,N)Au(Ph)和(P,N)Au(乙烯基)是关键中间体，它们负责烯醇的活化以及通过氧的外层亲核进攻使其环化。计算并比较了5-外向和6-内向路径，重现了实验观察到的4-戊烯-1-醇、(E)和(Z)-4-己烯-1-醇之间特殊的区域选择性差异。研究烯醇与金配位的方式（更多的η或η）在某些情况下可以提供一种预测环化优先路径的简单方法。
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