Paveliev Stanislav A, Segida Oleg O, Dvoretskiy Andrey, Terent'ev Alexander O
N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, 47 Leninsky prosp., Moscow 119991, Russian Federation.
ACS Omega. 2024 Dec 2;9(50):49825-49831. doi: 10.1021/acsomega.4c08532. eCollection 2024 Dec 17.
The electrochemically induced reaction between alkenes, bearing an allylic hydrogen atom, and -hydroxyphthalimide was investigated. Cross-dehydrogenative C-O coupling with phthalimide--oxyl radical, derived from -hydroxyphthalimide, occurs instead of oxidation of the allylic site, with the formation of a carbonyl group or functionalization of the double C=C bond. The discovered transformation proceeds in an undivided electrochemical cell equipped with a carbon felt anode and a platinum cathode. Coupling products were obtained with yields up to 79%. The developed process is based on the abstraction of hydrogen atom from the allylic position for functionalization while the C=C bond remains unreacted. The method exploits the ability of the phthalimide--oxyl radical to abstract hydrogen atoms with the following interception of the intermediate -centered radical.
研究了带有烯丙基氢原子的烯烃与N-羟基邻苯二甲酰亚胺之间的电化学诱导反应。与源自N-羟基邻苯二甲酰亚胺的邻苯二甲酰亚胺-N-氧基自由基发生交叉脱氢C-O偶联，而不是烯丙基位点的氧化，形成羰基或使碳-碳双键官能化。所发现的转化反应在配备有碳毡阳极和铂阴极的无隔膜电化学池中进行。偶联产物的产率高达79%。所开发的方法基于从烯丙基位置提取氢原子进行官能化，而碳-碳双键保持未反应状态。该方法利用邻苯二甲酰亚胺-N-氧基自由基提取氢原子的能力，随后截获以氮为中心的中间体自由基。
