Bischof Tobias, Guo Xueying, Krummenacher Ivo, Beßler Lukas, Lin Zhenyang, Finze Maik, Braunschweig Holger
Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg Am Hubland 97074 Würzburg Germany
Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg Am Hubland 97074 Würzburg Germany.
Chem Sci. 2022 Jun 2;13(25):7492-7497. doi: 10.1039/d2sc02750j. eCollection 2022 Jun 29.
The synthesis of 9-borafluorene with an electron-withdrawing -carboranyl substituent and its reactions with a series of alkenes are described. The -carboranyl substituent is bonded one of the cluster carbon atoms to the boron atom of the 9-borafluorene moiety. In all cases, the reactions afford partly saturated analogs of borepins ( 6,7-dihydroborepins) by unprecedented alkene insertion into the endocyclic B-C bond of the borole ring. Comparative studies with 9-bromo-9-borafluorene illustrate the superior insertion reactivity of the carboranyl-substituted derivative. A suite of experimental and computational techniques disclose the unique properties of the 9-borafluorene and provide insight into how the 9-carboranyl substituent affects its chemical reactivity.
本文描述了带有吸电子的 -碳硼烷基取代基的9-硼芴的合成及其与一系列烯烃的反应。-碳硼烷基取代基通过簇碳原子之一与9-硼芴部分的硼原子相连。在所有情况下，这些反应通过前所未有的烯烃插入硼杂环戊二烯环的内环B-C键，得到了部分饱和的硼环戊二烯类似物（6,7-二氢硼环戊二烯）。与9-溴-9-硼芴的对比研究表明了碳硼烷基取代衍生物具有更高的插入反应活性。一系列实验和计算技术揭示了9-硼芴的独特性质，并深入了解了9-碳硼烷基取代基如何影响其化学反应性。
