Investigations of the Copper-Catalyzed Oxidative Cross-Coupling of Tetrahydroisoquinolines with Diethylzinc by a Combination of Mass Spectrometric and Electrochemical Methods.
Investigations of the Copper-Catalyzed Oxidative Cross-Coupling of Tetrahydroisoquinolines with Diethylzinc by a Combination of Mass Spectrometric and Electrochemical Methods.
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DOI：
10.1002/chem.201704914
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发表时间：
2018-02
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影响因子：
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通讯作者：
J. A. Willms;Hermann Gleich;Michael Schrempp;D. Menche;M. Engeser
中科院分区：
文献类型：
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作者：
J. A. Willms;Hermann Gleich;Michael Schrempp;D. Menche;M. Engeser
采用电喷雾质谱（ESI-MS）研究了CuCl2催化四氢异喹啉（THIQs）与二乙基锌的有氧氧化交偶联反应。底物、中间体和产物易于检测。特别强调了CuCl2的作用。通过ESI- ms、电化学耦合ESI质谱（EC-MS）和循环伏安法（CV）对中间体的形成进行了更详细的研究。我们的实验一致地揭示了THIQ衍生物的n取代基及其相对于CuCl2的氧化稳定性的强烈影响。该结果有助于扩大反应的合成范围，同时也进一步确立了EC-MS在有机氧化还原反应机理研究中将质谱法与循环伏安法相结合的有价值的技术。
The aerobic oxidative cross-coupling of tetrahydroisoquinolines (THIQs) with diethylzinc catalyzed by CuCl2 has been examined by means of electrospray mass spectrometry (ESI-MS). Substrates, intermediates, and the product were readily detected. Particular emphasis has been placed on the role of CuCl2 . Formation of the intermediate iminium species has been investigated in more detail by ESI-MS, electrochemistry-coupled ESI mass spectrometry (EC-MS), and cyclic voltammetry (CV). Our experiments have consistently revealed strong influences of the N-substituent of the THIQ derivative and its oxidation stability with respect to CuCl2 . The results may help to expand the synthetic scope of the reaction, while also further establishing EC-MS as a valuable technique for linking mass spectrometry with cyclic voltammetry in mechanistic studies of organic redox reactions.