Dative Bonding Activation Enables Precise Functionalization of the Remote B–H Bond of nido-Carborane Clusters,Journal of the American Chemical Society

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Dative Bonding Activation Enables Precise Functionalization of the Remote B–H Bond of nido-Carborane Clusters
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-09-13 , DOI: 10.1021/jacs.4c10728
Hongyuan Ren ₁ , Ningning Zhou ₁ , Wenli Ma ₁ , Ping Zhang ₁ , Deshuang Tu ₁ , Chang-Sheng Lu ₁ , Hong Yan ₁

Affiliation

The innovation of synthetic strategies for selective B–H functionalization is a pivotal objective in the realm of boron cluster chemistry. However, the precise, efficient, and rapid functionalization of a B–H bond of carboranes that is distant from the existing functional groups remains intractable owing to the limited approaches for site-selective control from the established methods. Herein, we report a dative bonding activation strategy for the selective functionalization of a nonclassical remote B–H site of nido-carboranes. By leveraging the electronic effects brought by the exopolyhedral B(9)-dative bond, a cross-nucleophile B–H/S–H coupling protocol of the distal B(5)–H bond has been established. The dative bond not only amplifies the subtle reactivity difference among B–H bonds but also significantly changes the reactive sites, further infusing nido-carboranes with additional structural diversity. This reaction paradigm features mild conditions, rapid conversion, efficient production, broad scope, and excellent group tolerance, thus enabling the applicability to an array of complex bioactive molecules. The efficient and scalable reaction platform is amenable to the modular construction of photofunctional molecules and boron delivery agents for boron neutron capture therapy. This work not only provides an unprecedented solution for the selective diversification of distal B–H sites in nido-carboranes but also holds the potential for expediting the discovery of novel carborane-based functional molecules.

中文翻译：

配位键激活实现了 Nido-Carborane 簇远程 B-H 键的精确功能化

选择性 B-H 官能化合成策略的创新是硼簇化学领域的一个关键目标。然而，由于现有方法的位点选择性控制方法有限，远离现有官能团的碳硼烷 B-H 键的精确、高效和快速官能化仍然很棘手。在此，我们报告了一种用于选择性官能化nido -carborane 的非经典远程 B-H 位点的配位键激活策略。利用外多面体B(9)-配位键带来的电子效应，建立了远端B(5)-H键的跨亲核试剂B-H/S-H偶联方案。配位键不仅放大了B-H键之间微妙的反应性差异，而且还显着改变了反应位点，进一步为nido -carboranes注入了额外的结构多样性。该反应范式具有条件温和、转化快速、生产高效、范围广泛和优异的基团耐受性等特点，从而能够适用于一系列复杂的生物活性分子。高效且可扩展的反应平台适合用于硼中子捕获治疗的光功能分子和硼输送剂的模块化结构。这项工作不仅为nido -carborane中远端B-H位点的选择性多样化提供了前所未有的解决方案，而且还具有加速发现新型基于carborane的功能分子的潜力。

更新日期：2024-09-13

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