Department of Chemistry, University of Chicago, 929 East 57th, Street, Chicago, Illinois 60637, USA.
Faraday Discuss. 2017 Sep 8;201:303-315. doi: 10.1039/c7fd00030h.
We report here the synthesis of a robust and highly porous Fe-phenanthroline-based metal-organic framework (MOF) and its application in catalyzing challenging inter- and intramolecular C-H amination reactions. For the intermolecular amination reactions, a FeBr-metalated MOF selectively functionalized secondary benzylic and allylic C-H bonds. The intramolecular amination reactions utilizing organic azides as the nitrene source required the reduction of the FeBr-metalated MOF with NaBHEt to generate the active catalyst. For both reactions, Fe or Zr leaching was less than 0.1%, and MOFs could be recycled and reused with no loss in catalytic activity. Furthermore, MOF catalysts were significantly more active than the corresponding homogeneous analogs. This work demonstrates the great potential of MOFs in generating highly active, recyclable, and reusable earth abundant metal catalysts for challenging organic transformations.
我们在此报告一种坚固且高度多孔的基于 Fe-菲咯啉的金属-有机骨架（MOF）的合成及其在催化具有挑战性的分子间和分子内 C-H 氨化反应中的应用。对于分子间的氨化反应，FeBr 配位的 MOF 选择性地功能化仲苄基和烯丙基 C-H 键。利用有机叠氮化物作为氮宾源的分子内氨化反应需要用 NaBHEt 将 FeBr 配位的 MOF 还原以生成活性催化剂。对于这两种反应，Fe 或 Zr 的浸出量均小于 0.1%，并且 MOF 可以回收和再利用，而不会损失催化活性。此外，MOF 催化剂的活性明显高于相应的均相类似物。这项工作证明了 MOF 在生成高活性、可回收和可重复使用的丰富地球金属催化剂方面具有巨大的潜力，可用于具有挑战性的有机转化。
