Structure-Reactivity Relationships in Negishi Cross-Coupling Reactions

被引：30

作者：

Dong, Zhi-Bing ^{[2
]}

Manolikakes, Georg ^{[1
]}

Shi, Lei ^{[1
]}

Knochel, Paul ^{[1
]}

Mayr, Herbert ^{[1
]}

机构：

[1] Univ Munich, Dept Chem & Biochem, D-81377 Munich, Germany

[2] Jiangsu Univ, Sch Chem & Chem Engn, Zhenjiang 212013, Jiangsu, Peoples R China

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2010年 / 16卷 / 01期

关键词：

C-C bond formation; Hammett equation; kinetics; reaction mechanisms; substituent effects; MAGNESIUM EXCHANGE-REACTIONS; OXIDATIVE ADDITION; REDUCTIVE ELIMINATION; ZEROVALENT PALLADIUM; AROMATIC IODIDES; ACTIVE CATALYST; MECHANISM; REAGENTS; STEP; COMPLEXES;

D O I：

10.1002/chem.200902132

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Competition experiments have been performed to determine the relative reactivities of substituted bromobenzenes and of different arylzinc reagents in the [Pd(PPh3)(4)]-catalyzed Negishi cross-coupling reaction in THF at 25 degrees C. The cross-coupling reactions are accelerated by electron acceptors in the bromobenzenes, the effect of which increases in the order ortho < meta < para. On the other hand, electron acceptors in the arylzinc halides diminish the reaction rates. Hammett correlations show that substituent variations in the bromobenzenes (rho = +2.5) have a larger effect than substituent variations in the arylzinc halides (rho = -0.98).

引用

页码：248 / 253

页数：6

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