Efficient iron single-atom catalysts for selective ammoxidation of alcohols to nitriles

Abstract

Zeolitic imidazolate frameworks derived Fe1-N-C catalysts with isolated single iron atoms have been synthesized and applied for selective ammoxidation reactions. For the preparation of the different Fe-based materials, benzylamine as an additive proved to be essential to tune the morphology and size of ZIFs resulting in uniform and smaller particles, which allow stable atomically dispersed Fe–N4 active sites. The optimal catalyst Fe1-N-C achieves an efficient synthesis of various aryl, heterocyclic, allylic, and aliphatic nitriles from alcohols in water under very mild conditions. With its chemoselectivity, recyclability, high efficiency under mild conditions this new system complements the toolbox of catalysts for nitrile synthesis, which are important intermediates with many applications in life sciences and industry.

An enzyme-mimic single Fe-N 3 atom catalyst for the oxidative synthesis of nitriles via C─C bond cleavage strategy

“…9). As far as the oxidation of benzaldehyde into benzoic acid, the first step is the addition of one water to benzaldehyde to generate the geminal diol intermediate (12) (41), which underwent the consecutive release of two H atoms (─OH and ─CH) with the assistance of •O 2 − to give benzoic acid. On the similar way, the oxidative dehydrogenation of the two hydrogen atoms (─NH and ─CH) in aldimine intermediate (C 6 H 5 CH═NH) (10) generated benzonitrile.…”

“…Prominent methods include catalytic aerobic ammoxidation of primary alcohols or aldehydes into nitriles ( Fig. 1B ) ( 12 ). As for the construction of nitriles from secondary alcohols or ketones, the cleavage of C─C bond bearing high bond dissociation energy is inevitably involved ( 13 ).…”

Cu‐Oxide Nanoparticles Catalyzed Synthesis of Nitriles and Amides from Alcohols and Ammonia in Presence of Air

“…In this regard, different functionalized benzonitriles were synthesized. As an example, ether-, ester-, boronic-ester-, thio-ether-, primary amine-, N,N-dimethylamine-and cyano-substituted benzonitriles were selectively prepared starting from corresponding alcohols (Scheme 1, products [17][18][19][20][21][22][23][24][25][26].…”

“…In this regard, the preparation of nitriles from alcohols and ammonia by catalytic aerobic oxidations is considered to be an appropriate and green methodology. [ 17–28 ]…”

“…In this regard, the preparation of nitriles from alcohols and ammonia by catalytic aerobic oxidations is considered to be an appropriate and green methodology. [17][18][19][20][21][22][23][24][25][26][27][28] In general, the creation of an amide bond is of fundamental importance in organic synthesis, medicine, and biology. [8][9][10][11] Classically, primary amides are prepared by the reaction of activated carboxylic acid derivatives such as chlorides and anhydrides with ammonia or from carboxylic acids with ammonia in presence of coupling agents.…”