ReactNMR and ReactIR as Reaction Monitoring and Mechanistic Elucidation Tools: The NCS Mediated Cascade Reaction of α-Thioamides to α-Thio-β-chloroacrylamides
ReactNMR and ReactIR as Reaction Monitoring and Mechanistic Elucidation Tools: The NCS Mediated Cascade Reaction of α-Thioamides to α-Thio-β-chloroacrylamides
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DOI：
10.1021/jo201212p
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发表时间：
2011-12-02
影响因子：
3.6
通讯作者：
Kaerner, Andreas
中科院分区：
文献类型：
--
作者：
Foley, David A.;Doecke, Christopher W.;Kaerner, Andreas
流动反应IR和H-1 NMR反应监测，加上原位中间体表征，用于帮助N-氯琥珀酰亚胺介导的α-硫代酰胺转化的机理阐明。在这个反应级联中的多个中间体被识别和表征，并且特别地，提供了氯锍离子在α-硫代酰胺的氯化中的中间性的光谱证据。此外，溶剂对转化结果的影响进行了讨论。这项工作还证明了使用ReactIR和流动NMR反应监测（ReactNMR）的组合来表征复杂的多组分反应混合物的实用性。
On-flow ReactIR and H-1 NMR reaction monitoring, coupled with in situ intermediate characterization, was used to aid in the mechanistic elucidation of the N-chlorosuccinirnide mediated transformation of an alpha-athioarnide. Multiple intermediates in this reaction cascade are identified and characterized, and in particular, spectroscopic evidence for the intermediacy of the chlorosulfonium ion in the chlorination of alpha-thioamides is provided. Further to this, solvent effects on the outcome of the transformation are discussed. This work also demonstrates the utility of using a combination of ReactIR and flow NMR reaction monitoring (ReactNMR) for characterizing complex multicomponent reaction mixtures.