Chen Qianwei, Wang Minyan, Zhao Yue, Shi Zhuangzhi
State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China.
Nat Commun. 2025 Sep 1;16(1):8163. doi: 10.1038/s41467-025-63335-z.
Arenes bearing silyl and boryl, or germyl and boryl groups, represent a significant class of bifunctional molecules that have garnered considerable attention in organic synthesis due to their unique reactivity and versatility in undergoing diverse chemical transformations. Despite their importance, the synthesis of these mixed-metalloid compounds, particularly those with ortho-substituted aromatic frameworks, often involves complex, multi-step procedures. Herein, we present a highly efficient, single-step method for synthesizing ortho-boronated arylhydrosilanes and arylgermanes via catalytic C-H borylation reaction. The use of Si- and Ge-containing directing groups has been demonstrated to effectively suppress undesirable metathesis reactions, a side effect typically associated with their metallic nature. Our approach employs an iridium catalyst in combination with a ligand and an acetate base, which facilitates the formation of benzo-fused four-membered metallacycles within the catalytic cycle. The method's broad applicability and practicality are further underscored by its ability to generate a wide array of valuable intermediates that can be easily transformed into various functionalized molecules. Both experimental and computational studies provide profound insights into the reaction dynamics and the factors influencing the formation of these strained metallacycles.
带有甲硅烷基和硼基，或锗基和硼基的芳烃，是一类重要的双功能分子，由于其独特的反应活性和在多种化学转化中的多功能性，在有机合成中备受关注。尽管它们很重要，但这些混合准金属化合物的合成，特别是那些具有邻位取代芳族骨架的化合物，通常涉及复杂的多步程序。在此，我们提出了一种通过催化C-H硼化反应高效合成邻位硼化芳基氢硅烷和芳基锗烷的单步方法。含硅和锗的导向基团的使用已被证明能有效抑制不需要的复分解反应，这是通常与其金属性质相关的副作用。我们的方法使用铱催化剂与配体和乙酸盐碱相结合，这有助于在催化循环中形成苯并稠合的四元金属环。该方法能够生成大量可轻松转化为各种功能化分子的有价值中间体，进一步强调了其广泛的适用性和实用性。实验和计算研究都为反应动力学以及影响这些张力金属环形成的因素提供了深刻见解。
