Imada Yasushi, Röckl Johannes L, Wiebe Anton, Gieshoff Tile, Schollmeyer Dieter, Chiba Kazuhiro, Franke Robert, Waldvogel Siegfried R
Institute of Organic Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128, Mainz, Germany.
Department of Applied Biological Science, Tokyo University of Agriculture and Technology, Japan.
Angew Chem Int Ed Engl. 2018 Sep 10;57(37):12136-12140. doi: 10.1002/anie.201804997. Epub 2018 Jun 28.
A selective dehydrogenative electrochemical functionalization of benzylic positions that employs 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP) has been developed. The electrogenerated products are versatile intermediates for subsequent functionalizations as they act as masked benzylic cations that can be easily activated. Herein, we report a sustainable, scalable, and reagent- and metal-free dehydrogenative formal benzyl-aryl cross-coupling. Liberation of the benzylic cation was accomplished through the use of acid. Valuable diarylmethanes are accessible in the presence of aromatic nucleophiles. The direct application of electricity enables a safe and environmentally benign chemical transformation as oxidizers are replaced by electrons. A broad variety of different substrates and nucleophiles can be employed.
已开发出一种利用1,1,1,3,3,3-六氟-2-丙醇（HFIP）对苄基位置进行选择性脱氢电化学官能化的方法。电生成的产物是后续官能化的通用中间体，因为它们充当可轻松活化的掩蔽苄基阳离子。在此，我们报道了一种可持续、可扩展且无试剂和无金属的脱氢形式苄基-芳基交叉偶联反应。苄基阳离子的释放通过使用酸来实现。在芳香亲核试剂存在下可获得有价值的二芳基甲烷。直接施加电能实现安全且环境友好的化学转化，因为氧化剂被电子所取代。可以使用各种各样不同的底物和亲核试剂。
