Zheng Danqing, Plöger Stefanie, Daniliuc Constantin G, Studer Armido
Westfälische Wilhelms-Universität, Organisch-Chemisches Institut, Corrensstrasse 40, 48149, Münster, Germany.
Angew Chem Int Ed Engl. 2021 Apr 6;60(15):8547-8551. doi: 10.1002/anie.202016955. Epub 2021 Feb 25.
An atom-economic intermolecular radical addition reaction of acyloxy nitroso compounds to electron-deficient alkenes mediated by visible light is reported. The starting nitroso derivatives are readily prepared by oxidation of the corresponding oximes prepared from ketones and the overall transformation represents an oxidative coupling of a ketone with a Michael acceptor. The cascade proceeds smoothly under mild conditions, providing a series of valuable functionalized oximes in moderate to good yields. Mechanistic studies suggest that these cascades proceed via addition/coupling processes that are controlled by the persistent radical effect (PRE) with NO acting as the persistent species.
报道了一种可见光介导的酰氧基亚硝基化合物与缺电子烯烃的原子经济分子间自由基加成反应。起始亚硝基衍生物可通过氧化由酮制备的相应肟轻松制得，整个转化过程代表了酮与迈克尔受体的氧化偶联。该串联反应在温和条件下顺利进行，以中等至良好的产率提供了一系列有价值的官能化肟。机理研究表明，这些串联反应通过加成/偶联过程进行，该过程由持久自由基效应（PRE）控制，其中NO作为持久物种。
