Mechanistic Insights about the Ligand-Enabled Oxy-arylation/vinylation of Alkenes via Au(I)/Au(III) Catalysis

被引：12

作者：

Rigoulet, Mathilde ^{[1
]}

Miqueu, Karinne ^{[2
]}

Bourissou, Didier ^{[1
]}

机构：

[1] Univ Paul Sabatier, CNRS, UPS Lab Heterochim Fondamentale & Appl, LHFA UMR 5069, 118 Route Narbonne, F-31062 Toulouse, France

[2] Univ Pau & Pays lAdour, CNRS, E2S UPPA Inst Sci Analyt & Phys Chim Environm & M, IPREM UMR 5254, Helioparc,2 Ave President Angot, F-64053 Pau 09, France

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2022年 / 28卷 / 60期

关键词：

complex density; functional theory; gold; mechanism; regioselectivity; VISIBLE-LIGHT PHOTOREDOX; REDUCTIVE ELIMINATION; OXIDATIVE ADDITION; GOLD; REACTIVITY; HYDROAMINATION; OXYARYLATION; COMPLEXES; METALS; ORIGIN;

D O I：

10.1002/chem.202202110

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mechanism of oxy-arylation/vinylation of alkenes catalyzed by the (MeDalphos)AuCl complex was comprehensively investigated by DFT. (P,N)Au(Ph)(2+) and (P,N)Au(vinyl)(2+) 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 eta(2) or eta(1)) can offer, in some cases, a simple way to predict the favored path of cyclization.

引用

页数：12

共 9 条

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