Xiao Xiang, Shen Kesheng, Jing Xu, Duan Chunying
State Key Laboratory of Fine Chemicals, College of Chemistry, Dalian University of Technology, 116024, P. R. China.
Dalton Trans. 2024 Jul 30;53(30):12604-12609. doi: 10.1039/d4dt01332h.
The activation and selective functionalization of inert C(sp)-H bonds is fundamental for industrial applications and occupies a very important place in industry, but it remains a great challenge in current synthetic chemistry. In this paper, we report an approach for activating reactive -butyl peroxyl radicals by modifying Ru-porphyrin into metal-organic frameworks (MOFs) for the activation of inert C(sp)-H bonds. Under mild conditions, the Ru-porphyrinyl MOF can activate the peroxyl radical, extracting a hydrogen atom from the inert C(sp)-H bond. Mn paddlewheels with unsaturated coordination sites were introduced into the MOF, and direct oxidative conversion using environmentally friendly oxygen provides a new pathway to activate the inert C(sp)-H bond.
惰性C(sp) - H键的活化和选择性官能团化对于工业应用至关重要，在工业中占据着非常重要的地位，但在当前的合成化学中仍然是一个巨大的挑战。在本文中，我们报道了一种通过将钌卟啉修饰成金属有机框架（MOF）来活化反应性叔丁基过氧自由基以实现惰性C(sp) - H键活化的方法。在温和条件下，钌卟啉基MOF能够活化过氧自由基，从惰性C(sp) - H键中提取一个氢原子。将具有不饱和配位位点的锰桨轮引入到MOF中，利用环境友好的氧气进行直接氧化转化为活化惰性C(sp) - H键提供了一条新途径。
