C–C Bond Activation and Demethylenation of Epoxides by Amine Radical Dications
C–C Bond Activation and Demethylenation of Epoxides by Amine Radical Dications
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胺自由基双阳离子对环氧化物的 C–C 键激活和脱甲基化
DOI：
10.1021/acs.joc.3c00605
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Dudding, Travis
中科院分区：
文献类型：
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作者：
Holt, Eric;Garrison, Nathaniel G.;Rowshanpour, Rozhin;Kim, Justin Jeeyoung;Henriquez, Nicolas;Lam, Winson;Kiame, Neil;Williams, Jack;Zhao, Sherrie;Dudding, Travis
在这篇文章中，我们探索了一种独特的反应模式，涉及一种罕见的基于自由基的C-C键断裂的环氧化物，然后脱亚甲基化。该反应是由Selecfluor和其自由基阳离子串联工作完成的;提出了一种由实验和DFT计算支持的机制，该机制涉及关键反应中间体的生成和鉴定。该反应似乎对1，1-二取代环氧化物相当普遍。
In this note, we explore a unique reactivity pattern that involves a rare radical-based C–C bond scission of epoxides followed by demethylenation. The reaction is accomplished by Selecfluor and its radical dication working in tandem; a mechanism supported by experiment and DFT calculations is proposed that involves the generation and identification of a key reactive intermediate. The reaction seems to be fairly general for 1,1-disubstituted epoxides.