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Electrochemical Intramolecular Aminooxygenation of Unactivated Alkenes

机译:未活化烯烃的电化学分子内氨基氧化

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摘要

An electrochemical approach to the intramolecular aminooxygenation of unactivated alkenes has been developed. This process is based on the addition of nitrogen-centered radicals, generated through electrochemical oxidation, to alkenes followed by trapping of the cyclized radical intermediate with 2,2,6,6-tetramethylpiperidine-Noxyl radical (TEMPO). Difunctionalization of a variety of alkenes with easily available carbamates/amides and TEMPO affords aminooxygenation products in high yields and with excellent trans selectivity for cyclic systems (d.r. up to>20:1). The approach provides a much-needed complementary route to existing cis-selective methods.
机译:已开发出一种用于未活化烯烃的分子内氨基加氧的电化学方法。该方法基于通过电化学氧化将以氮为中心的自由基加到烯烃中,然后用2,2,6,6-四甲基哌啶-Noxyl自由基(TEMPO)捕获环化的自由基中间体。用容易获得的氨基甲酸酯/酰胺和TEMPO对各种烯烃进行双官能化可提供高收率的氨基氧合产物,并且对环状系统具有出色的反式选择性(d.r.高达> 20:1)。该方法为现有的顺式选择方法提供了急需的补充途径。

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