Electron-transfer-catalyzed dimerization of trans-anethole: detection of the distonic tetramethylene radical cation intermediate by extractive electrospray ionization mass spectrometry.
Electron-transfer-catalyzed dimerization of trans-anethole: detection of the distonic tetramethylene radical cation intermediate by extractive electrospray ionization mass spectrometry.
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DOI：
10.1021/ja806791c
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发表时间：
2008-12
影响因子：
15
通讯作者：
Cesar A Marquez;Hao‐Yang Wang;Francesco Fabbretti;J. Metzger
中科院分区：
文献类型：
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作者：
Cesar A Marquez;Hao‐Yang Wang;Francesco Fabbretti;J. Metzger
采用EESI脱溶液滴作为微反应器，在毫秒时间范围内对凝析液相的短时间瞬态反应进行质谱研究。研究了电子转移催化的反式茴香醚二聚化反应，分离了自由基阳离子链反应的中间体，并用质谱联用技术对其进行了表征。检测到中间产物为双离子四亚甲基自由基阳离子3(o)(*+)，并观察到其环化生成环丁烷自由基阳离子3(c)(*+)，这有力地证明了反应是逐步发生的。
The desolvating droplets of EESI were used as microreactor for the mass spectrometric study of short-lived transients of reactions in condensed liquid phase in the millisecond time region. The electron-transfer-catalyzed dimerization of trans-anethole was investigated and the intermediates in the radical cation chain reaction were isolated and characterized by MS-MS. The distonic tetramethylene radical cation 3(o)(*+) was detected as intermediate, and its cyclization to give the cyclobutane radical cation 3(c)(*+) was observed giving strong evidence that the reaction takes place stepwise.