<p>Ammoxidation of methylarenes using ammonia and air is the main method for the synthesis of aromatic nitriles in the chemical industry. Despite significant efforts in industry and academia, no general and selective catalyst based on less toxic and earth-abundant metals has been developed for this reaction. Here we report a single-atom iron-based material (Fe@BNC-800-L1) with Fe–N<sub>5</sub>–B<sub><i>x</i></sub> configuration as an efficient <i>sp</i><sup>3</sup>-hybridized C–H- and C–C bond oxidation catalyst. Due to the presence of Fe<sup>3+</sup>, B and N species, which are co-embedded in the micro-mesoporous carbon matrix, these materials show excellent activity for ammoxidation of methyl-substituted (hetero)arenes. Furthermore, highly selective C–C bond cleavage reactions of alkylarenes are presented, which complement the toolbox for nitrile synthesis. The generality of this presented Fe-based ammoxidation methodology is showcased by the straightforward and selective synthesis of &gt;60 functionalized and structurally diverse nitriles, which are important precursors and key intermediates in organic synthesis with many applications in life sciences and industry.</p><p></p>

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Iron-based single-atom catalysts for selective ammoxidation of C(sp3)–H bonds and oxidative C–C cleavage reactions

  • Zhuang Ma,
  • Nils Rockstroh,
  • Zupeng Chen,
  • Vishakha Goyal,
  • Chakreshwara Kuloor,
  • Stephan Bartling,
  • Zdeněk Baďura,
  • Jabor Rabeah,
  • Lin Dong,
  • Henrik Lund,
  • Bing Nan,
  • Radek Zbořil,
  • Rajenahally V. Jagadeesh,
  • Matthias Beller

摘要

Ammoxidation of methylarenes using ammonia and air is the main method for the synthesis of aromatic nitriles in the chemical industry. Despite significant efforts in industry and academia, no general and selective catalyst based on less toxic and earth-abundant metals has been developed for this reaction. Here we report a single-atom iron-based material (Fe@BNC-800-L1) with Fe–N5–Bx configuration as an efficient sp3-hybridized C–H- and C–C bond oxidation catalyst. Due to the presence of Fe3+, B and N species, which are co-embedded in the micro-mesoporous carbon matrix, these materials show excellent activity for ammoxidation of methyl-substituted (hetero)arenes. Furthermore, highly selective C–C bond cleavage reactions of alkylarenes are presented, which complement the toolbox for nitrile synthesis. The generality of this presented Fe-based ammoxidation methodology is showcased by the straightforward and selective synthesis of >60 functionalized and structurally diverse nitriles, which are important precursors and key intermediates in organic synthesis with many applications in life sciences and industry.