DFT Investigation of the Palladium-Catalyzed Ene-Yne Coupling

被引：13

作者：

Henriksen, Signe Teuber ^{[2
]}

Tanner, David ^{[2
]}

Skrydstrup, Troels ^{[3
,4
]}

Norrby, Per-Ola ^{[1
]}

机构：

[1] Univ Gothenburg, Dept Chem, S-41296 Gothenburg, Sweden

[2] Tech Univ Denmark, Dept Chem, DK-2800 Lyngby, Denmark

[3] Aarhus Univ, Ctr Insoluble Prot Struct inSPIN, Dept Chem, DK-8000 Aarhus, Denmark

[4] Aarhus Univ, Interdisciplinary Nanosci Ctr, DK-8000 Aarhus, Denmark

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2010年 / 16卷 / 31期

关键词：

density functional calculations; ene-yne coupling; homogeneous catalysis; palladium; reaction mechanisms; CONTINUUM DIELECTRIC THEORY; HECK REACTION; OXIDATIVE ADDITION; ELECTRONIC CONTROL; ARYL CHLORIDES; SOLVATION; COMPLEXES; MECHANISM; REGIOCHEMISTRY; ARYLATION;

D O I：

10.1002/chem.201001158

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mechanism of the recently developed palladium-catalyzed ene-yne coupling has been evaluated by DFT methods. The calculations validate the previously proposed reaction mechanism and explain the stereoselectivity of the reaction (exclusive formation of the E isomer of the disubstituted alkene). Concerning chemoselectivity, the calculations also clarify why the ene-yne coupling is able to dominate over plausible alternative reaction pathways such as alkene homocoupiing and alkyne polymerization. The role of the phosphine ligand at various stages of the catalytic cycle has also been delineated.

引用

页码：9494 / 9501

页数：8

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