DFT Studies on the Palladium-Catalyzed Dearomatization Reaction between Chloromethylnaphthalene and the Cyclic Amine Morpholine
DFT Studies on the Palladium-Catalyzed Dearomatization Reaction between Chloromethylnaphthalene and the Cyclic Amine Morpholine
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钯催化氯甲基萘与环胺吗啉脱芳构化反应的DFT研究
DOI：
10.1021/om301215a
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发表时间：
2013-04
期刊：
影响因子：
2.8
通讯作者：
林振阳
中科院分区：
文献类型：
--
作者：
谢湖均;Zhang, Hong;林振阳
采用密度泛函理论研究了钯催化氯甲基萘与环胺吗啉脱芳构化反应的机理。计算结果表明，脱芳产物的还原消除是通过η3-exo-（萘基）甲基配体的帕拉碳与酰胺配体的氮原子之间的分子内C-N键偶联进行的.自由能垒仅为13.1 kcal/mol，明显低于原先认为的η3-内-（萘基）甲基中间体的自由能垒（37.8 kcal/mol）。为了比较，各种C-N偶联反应路径导致形成脱芳和芳族产物也已被检查。
Density functional theory calculations have been performed to investigate the mechanisms of the Pd-catalyzed dearomatization reaction between chloromethylnaphthalene and the cyclic amine morpholine. The calculation results indicate that the reductive elimination leading to the formation of the dearomatic product takes place via an intramolecular C–N bond coupling between the para carbon of an η3-exo-(naphthyl)methyl ligand and the nitrogen atom of the amide ligand. The free energy barrier is calculated to be only 13.1 kcal/mol, significantly lower than that (37.8 kcal/mol) through the η3-endo-(naphthyl)methyl intermediate originally thought. For comparison, various C–N coupling reaction pathways leading to the formation of dearomatic and aromatic products have also been examined.
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