The role of chelating diamine ligands in the Goldberg reaction: A kinetic study on the copper-catalyzed amidation of aryl iodides
The role of chelating diamine ligands in the Goldberg reaction: A kinetic study on the copper-catalyzed amidation of aryl iodides
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DOI：
10.1021/ja050120c
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发表时间：
2005-03-30
影响因子：
15
通讯作者：
Buchwald, SL
中科院分区：
文献类型：
--
作者：
Strieter, ER;Blackmond, DG;Buchwald, SL
介绍了铜催化芳基碘化物酰胺化反应的机理。动力学数据表明，二胺配体可以防止酰胺的多次连接。在催化循环外形成氨基甲酸酯有助于使对二胺浓度的依赖合理化，以及在低二胺浓度下对酰胺浓度的反向依赖。通过Cu(I)酰胺的化学和动力学能力确定了它的中间作用。
The mechanistic details of the Cu-catalyzed amidation of aryl iodides are presented. The kinetic data suggest that the diamine ligand prevents multiple ligation of the amide. The formation of an amidocuprate species external to the catalytic cycle helped to rationalize the dependence on diamine concentration and the inverse dependence on amide concentration at low diamine concentrations. The intermediacy of a Cu(I) amidate was established through both its chemical and kinetic competency.