Wang Yefei, Zhao Liang, Ji Guanfeng, He Cheng, Liu Songtao, Duan Chunying
State Key Laboratory of Fine Chemicals, Zhang Dayu School of Chemistry, Dalian University of Technology, Dalian 116024, P. R. China.
ACS Appl Mater Interfaces. 2022 Jan 19;14(2):2794-2804. doi: 10.1021/acsami.1c20420. Epub 2022 Jan 6.
Activation and selective functionalization of inert C(sp)-H bonds remain one of the most challenging tasks in current synthetic chemistry. Herein, by decorating vanadium(V)-porphyrin into metal-organic frameworks (MOFs) to stabilize the active tertbutyl peroxide radical, we reported a new approach to accomplish inert C(sp)-H bond activation by a synergistic bimetallic strategy via a hydrogen atom transfer process under mild conditions. The stabilized peroxide radical by V-porphyrin-based MOFs abstracted a hydrogen atom from the inert C(sp)-H bonds for direct oxidization transformation utilizing environmentally friendly oxygen. Taking advantage of the high stability of Zr clusters, the new Zr-MOF was recyclable six times without a conversion efficiency decrease. From this foundation, {Mn(μ-O)} cluster nodes with potential unsaturated coordinated sites were introduced into MOFs to replace Zr clusters, realizing the pre-activation of substrates through the interaction between Mn nodes and substrates. The synergistic bimetallic activation effect of V-porphyrin and Mn nodes dramatically promoted the conversion efficiency and product selectivity for inert C(sp)-H bond functionalization.
惰性C(sp) - H键的活化和选择性官能团化仍然是当前合成化学中最具挑战性的任务之一。在此，通过将钒(V) - 卟啉修饰到金属有机框架(MOF)中以稳定活性叔丁基过氧化物自由基，我们报道了一种新方法，即在温和条件下通过氢原子转移过程，采用双金属协同策略实现惰性C(sp) - H键的活化。基于钒卟啉的MOF稳定的过氧化物自由基从惰性C(sp) - H键中提取氢原子，利用环境友好的氧气进行直接氧化转化。利用Zr簇的高稳定性，新型Zr - MOF可循环使用六次而不降低转化效率。在此基础上，将具有潜在不饱和配位位点的{Mn(μ - O)}簇节点引入MOF中以取代Zr簇，通过Mn节点与底物之间的相互作用实现底物的预活化。钒卟啉和Mn节点的双金属协同活化效应显著提高了惰性C(sp) - H键官能团化的转化效率和产物选择性。
