Beck Eva, Bröllos Diana, Krummenacher Ivo, Kupfer Thomas, Dietz Maximilian, Wellnitz Tim, Mihm Cornelius, Braunschweig Holger
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, Würzburg, Germany.
Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, Würzburg, Germany.
Nat Commun. 2025 Jun 12;16(1):5304. doi: 10.1038/s41467-025-60549-z.
While small carbocyclic rings have long been recognized as pivotal building blocks in chemistry, their all-boron counterparts have remained largely unexplored. In this work, we present a detailed account of the functionalization reactivity of our cyclic tetraborane B(NCy) (Cy = cyclohexyl) encompassing both ring-expansion and ring-opening reactions. Specifically, diphenyl dichalcogenides effect ring expansion to five-membered BE rings (E = S, Se, Te), while halogenating agents induce ring opening to generate linear tetraboranes with halide end groups. These transformations reveal reactivity patterns reminiscent of strained organic ring systems, thus highlighting the cyclic tetraborane's potential as a versatile precursor for synthesizing intricate boron-rich architectures.
虽然小碳环长期以来一直被认为是化学中的关键构建块，但其全硼类似物在很大程度上仍未得到探索。在这项工作中，我们详细阐述了环状四硼烷B(NCy)（Cy = 环己基）的官能化反应活性，包括扩环和开环反应。具体而言，二苯基二硫属化物会使环扩展为五元BE环（E = S、Se、Te），而卤化剂会引发开环反应，生成带有卤化物端基的线性四硼烷。这些转化揭示了类似于张力有机环体系的反应模式，从而突出了环状四硼烷作为合成复杂富硼结构通用前体的潜力。
