Department of Organic Chemistry, University of Regensburg, Universitätsstraße 31, 93053, Regensburg, Germany.
Department of Chemistry, Umeå University, KB.C4, Linnaeus väg 10, 901 87, Umeå, Sweden.
Angew Chem Int Ed Engl. 2019 Jun 17;58(25):8577-8580. doi: 10.1002/anie.201902473. Epub 2019 May 22.
We report the visible-light-mediated synthesis of β-chloro ketones from aryl cyclopropanes, oxygen, hydrochloric acid, and nitric acid. The operationally simple and catalyst-free method uses cheap standard laboratory reagents and displays broad functional-group tolerance. Moreover, scale up of the reaction and late-stage functionalization of bioactive compounds is possible, providing the opportunity to utilize the cyclopropane ring as a masked β-chloro ketone in a reaction sequence. We propose a light-driven radical chain reaction initiated by the reaction of diluted hydrochloric and nitric acid to produce small quantities of molecular chlorine. The mechanistic hypothesis is supported by O labelling and UV/Vis experiments, cyclovoltammetry, and several control reactions.
我们报告了一种可见光介导的从芳基环丙烷、氧气、盐酸和硝酸中合成β-氯酮的方法。该方法操作简单，无需催化剂，使用廉价的标准实验室试剂，具有广泛的官能团耐受性。此外，反应的放大和生物活性化合物的后期官能化是可行的，为在反应序列中利用环丙烷环作为掩蔽的β-氯酮提供了机会。我们提出了一种由盐酸和硝酸稀释反应引发的光驱动自由基链反应，以产生少量的氯气。该机理假设得到了 O 标记和 UV/Vis 实验、循环伏安法和几个对照反应的支持。
