碳硼烷硼顶点选择性亲核取代反应

碳硼烷是一类由两个碳氢及十个硼氢顶点组成的笼状分子, 在医学、材料、配位化学和金属有机化学等领域都有重要的应用, 因此发展高效、简便的方法高选择性获取碳硼烷官能化衍生物具有重要的理论和现实意义. 近年来, 通过亲电取代、过渡金属催化、亲核取代等策略, 实现了碳硼烷硼–氢键高效、高选择性官能化. 本文根据硼–氢键的不同反应位点, 评述了利用亲核取代反应策略进行碳硼烷选择性官能团化的研究进展, 详细讨论了反应底物普适性、选择性控制及反应机理, 并对该领域后续研究所面临的挑战和发展前景进行了展望.

Carboranes are a class of polyhedral carbon-boron molecular clusters featuring three-dimensional (3D) aromaticity, which are often considered as 3D analogues to benzene. They are finding wide applications as useful functional building blocks in medicine, materials and coordination/organometallic chemistry. Thus, selective functionalization of carboranes has received tremendous research interest. Over the years, three major strategies (electrophilic cage BH substitution, transition metal catalyzed cage BH functionalization, and nucleophilic cage BH substitution) have been developed for selective cage BH functionalization of carboranes. The former two strategies have been covered in several review articles. In this review, we summarize the advance on selective functionalization of carboranes via nucleophilic cage BH substitution strategy. The reaction scope, selectivity control and reaction mechanism are discussed in detail. In addition, the opportunities and challenges in this field of research are also commented.