Ruthenium-Catalyzed Oxidative Coupling/Cyclization of Isoquinolones with Alkynes through C-H/N-H Activation: Mechanism Study and Synthesis of Dibenzo[a,g]quinolizin-8-one Derivatives

被引：107

作者：

Li, Bin ^{[1
]}

Feng, Huiliang ^{[1
]}

Wang, Nuancheng ^{[1
]}

Ma, Jianfeng ^{[1
]}

Song, Haibin ^{[1
]}

Xu, Shansheng ^{[1
]}

Wang, Baiquan ^{[1
,2
]}

机构：

[1] Nankai Univ, Coll Chem, State Key Lab Elementoorgan Chem, Tianjin 300071, Peoples R China

[2] Chinese Acad Sci, State Key Lab Organometall Chem, Shanghai 200032, Peoples R China

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2012年 / 18卷 / 40期

关键词：

C-H activation; C-C coupling; oxidation; reaction mechanisms; ruthenium; INTERNAL ALKYNES; BOND FORMATION; CARBON-CARBON; O BOND; RH; PALLADIUM; ARYLATION; INSERTION; FUNCTIONALIZATIONS; HETEROCYCLES;

D O I：

10.1002/chem.201201862

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mechanism of [{RuCl2-(p-cymene)}(2)]-catalyzed oxidative annulations of isoquinolones with alkynes was investigated in detail. The first step is an acetate-assisted C-H bond activation process to form cyclometalated compounds. Subsequent mono-alkyne insertion of the Ru-C bonds of the cyclometalated compounds then takes place. Finally, oxidative coupling of the C-N bond of the insertion compounds occurs to afford Ru-0 sandwich complexes that undergo oxidation to regenerate the catalytically active Ru-II complex with the copper oxidant and release the desired dibenzo[a,g]quinolizin-8-one derivatives. All of the relevant intermediates were fully characterized and determined by single crystal X-ray diffraction analysis. The [{RuCl2(p-cymene)}(2)]-catalyzed C-H bond functionalization of isoquinolones with alkynes to synthesize dibenzo[a,g]quinolizin-8-one derivatives through C-H/N-H activation was also demonstrated.

引用

页码：12873 / 12879

页数：7

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