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Ammoxidation: History
Please note this is an old version of this entry, which may differ significantly from the current revision.
Subjects: Chemistry, Organic
Contributor: Helena Kang

Ammoxidation is an oxidative nitrogen-incorporation process in which a hydrocarbon or heteroatom-substituted substrate reacts with ammonia and an oxidant, typically molecular oxygen, to furnish a nitrile or, under modified conditions, a primary amide. Classically, an alkene or alkylarene is converted to the corresponding nitrile at a mixed-metal oxide surface; the same formal transformation can be effected on alcohols and carboxylic acids with molecular catalysts. Iron single-atom catalysts mediate selective ammoxidation of alcohols to nitriles, coupling dehydrogenation with nitrogen transfer from ammonia [1]. Copper-catalyzed aerobic decarboxylative ammoxidation of phenylacetic acids yields primary amides rather than nitriles, showing that the nitrogenous oxidation level is catalyst- and substrate-dependent [2]. Carboxylic acid-modified metal oxides allow the product distribution between nitrile and amide to be tuned under aerobic conditions [3]. The defining stoichiometric feature is concurrent oxidation and C–N bond formation using NH3 as the nitrogen source, which distinguishes ammoxidation from simple amination (no net oxidation) and from aerobic oxidation that does not incorporate nitrogen.

  • ammoxidation
  • nitrile synthesis
  • aerobic oxidation
  • ammonia

Synthesis and Catalytic Reactions • Organic Chemistry • Chemistry • Physical Sciences

References

  1. Kangkang Sun; Hongbin Shan; Helfried Neumann; Guo-Ping Lu; Matthias Beller; Efficient iron single-atom catalysts for selective ammoxidation of alcohols to nitriles. Nat. Commun. 2022, 13, 1-9, 10.1038/s41467-022-29074-1.
  2. Qiuling Song; Qiang Feng; Kai Yang; Synthesis of Primary Amides via Copper-Catalyzed Aerobic Decarboxylative Ammoxidation of Phenylacetic Acids and α-Hydroxyphenylacetic Acids with Ammonia in Water. Org. Lett. 2014, 16, 624-627, 10.1021/ol403586c.
  3. Xiuquan Jia; Jiping Ma; Fei Xia; Yongming Xu; Jin Gao; Jie Xu; Carboxylic acid-modified metal oxide catalyst for selectivity-tunable aerobic ammoxidation. Nat. Commun. 2018, 9, 1-7, 10.1038/s41467-018-03358-x.
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