Mechanistic Study of Gold(I)-Catalyzed Hydroamination of Alkynes: Outer or Inner Sphere Mechanism?

被引：69
|
作者：
Zhdanko, Alexander [1 ]
Maier, Martin E. [1 ]
机构：
[1] Univ Tubingen, Inst Organ Chem, D-72076 Tubingen, Germany
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2014年 / 53卷 / 30期
关键词：
gold catalysis; hydroamination; reaction mechanisms; GOLD-CATALYZED HYDROAMINATION; INTRAMOLECULAR HYDROAMINATION; INTERMOLECULAR HYDROAMINATION; COORDINATION CHEMISTRY; TRANSITION-METAL; N-HETEROCYCLES; ACID CATALYSIS; BRONSTED ACID; ALLENES; CYCLIZATION;
D O I：
10.1002/anie.201402557
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
An experimental mechanistic study of the gold(I)catalyzed hydroamination shows the formation of conformationally flexible auro-iminium salts Au-Im, which originate from the protonation of a vinyl gold species. Rotation around the C-CAu bond is the reason for the loss of stereospecificity of protodeauration, which explains the stereochemical result of the Stradiotto reaction. The ambiguity about inner or outer sphere mechanism is thus resolved in favor of the outer sphere mechanism.
引用
收藏
页码：7760 / 7764
页数：5
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