Wang Yefei, Zhou Zhen, Zhao Liang, He Cheng, Sun Wenlong, Duan Chunying
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, P. R. China.
State Key Laboratory of Fine Chemicals, Zhang Dayu School of Chemistry, Dalian University of Technology, Dalian 116024, P. R. China.
ACS Appl Mater Interfaces. 2021 Mar 10;13(9):10925-10932. doi: 10.1021/acsami.0c22276. Epub 2021 Feb 24.
The activation and transformation of inert alkyl C(sp)H bonds to obtain high-value fine chemicals by sustainable solar energy are of great significance. Herein, by incorporating Ir-porphyrin into metal-organic frameworks (MOFs) to stabilize the highly active carbene, we reported a new approach to combining metallo- and photocatalysis to efficiently accelerate carbene migratory insertion and CH bond activation the radical coupling pathway for inert alkane functionalization. The -formed carbene was restricted into the pores of MOFs to produce Ir-carbene, allowing the first-time isolation and structural characterization of the Ir-carbene intermediate which are not stabilized by a heteroatom. The product of the reaction, especially the cyclic ethers as substrates, suggested that the functionalization of the α position of the alkoxy group was favored. Additionally, the new approach could be extended to stabilize the metal carbene intermediates to realize C(sp)H bond alkylation and arylation.
通过可持续太阳能将惰性烷基C(sp)H键活化和转化以获得高价值精细化学品具有重要意义。在此，通过将铱卟啉掺入金属有机框架（MOF）中以稳定高活性卡宾，我们报道了一种将金属催化和光催化相结合的新方法，以有效加速卡宾迁移插入和CH键活化——惰性烷烃官能化的自由基偶联途径。生成的卡宾被限制在MOF的孔中以生成铱卡宾，首次实现了未被杂原子稳定的铱卡宾中间体的分离和结构表征。反应产物，尤其是作为底物的环醚，表明烷氧基α位的官能化是有利的。此外，这种新方法可以扩展到稳定金属卡宾中间体以实现C(sp)H键烷基化和芳基化。
