Mechanistic Study of the Titanocene(III)-Catalyzed Radical Arylation of Epoxides

被引：61

作者：

Gansaeuer, Andreas ^{[1
]}

von Laufenberg, Daniel ^{[1
]}

Kube, Christian ^{[1
]}

Dahmen, Tobias ^{[1
]}

Michelmann, Antonius ^{[1
]}

Behlendorf, Maike ^{[1
]}

Sure, Rebecca ^{[2
]}

Seddiqzai, Meriam ^{[2
]}

Grimme, Stefan ^{[2
]}

Sadasivam, Dhandapani V. ^{[3
]}

Fianu, Godfred D. ^{[3
]}

Flowers, Robert A., II ^{[3
]}

机构：

[1] Univ Bonn, Kekule Inst Organ Chem & Biochem, D-53121 Bonn, Germany

[2] Univ Bonn, Inst Phys Chem & Theoret Chem, Mulliken Ctr Theoret Chem, D-53115 Bonn, Germany

[3] Lehigh Univ, Dept Chem, Bethlehem, PA 18015 USA

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2015年 / 21卷 / 01期

基金：

美国国家科学基金会;

关键词：

arylation; cyclic voltammetry; DFT; epoxides; radicals; titanium; ABSOLUTE RATE CONSTANTS; CATALYZED 5-EXO CYCLIZATIONS; ZETA VALENCE QUALITY; ALKYL RADICALS; DENSITY FUNCTIONALS; 4-EXO CYCLIZATIONS; BASIS-SETS; THERMOCHEMICAL KINETICS; NUCLEOPHILIC CHARACTER; HOMOGENEOUS CATALYSIS;

D O I：

10.1002/chem.201404404

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

An atom-economical and catalytic arylation of epoxide-derived radicals is described. The key step of the catalytic system is a sequential electron and proton transfer for the rearomatization of the radical sigma-complex and catalyst regeneration. Kinetic, computational, spectroscopic, and cyclovoltammetric investigations highlight the key issues of the reaction mechanism and catalyst stabilization by collidine hydrochloride. Studies employing radicophiles rule out the participation of cations as reactive intermediates.

引用

页码：280 / 289

页数：10

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