Electrochemical Nonacidic N‐Nitrosation/N‐Nitration of Secondary Amines through a Biradical Coupling Reaction

An acid‐free N‐nitrosation/nitration of the N−H bonds in secondary amines with Fe(NO3)3 ⋅ 9H2O as the nitroso/nitro source through an electrocatalyzed radical coupling reaction was developed. Cyclic aliphatic amines and N‐heteroaromatic compounds were N‐nitrosated and N‐nitrated, respectively, under...

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Bibliographic Details
Published in:Advanced synthesis & catalysis 2020-11, Vol.362 (22), p.5036-5043
Main Authors: Zhao, Ji‐Ping, Ding, Lu‐jia, Wang, Peng‐Cheng, Liu, Ying, Huang, Min‐Jun, Zhou, Xin‐Li, Lu, Ming
Format: Article
Language:English
Subjects:
Aliphatic amines
Coupling (molecular)
electrochemistry, N−N bond formation
Heterocyclic compounds
Hydrogen bonds
N-nitrosation, N-nitration
Nitration
Nitro compounds
radical addition
Selectivity
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Summary:An acid‐free N‐nitrosation/nitration of the N−H bonds in secondary amines with Fe(NO3)3 ⋅ 9H2O as the nitroso/nitro source through an electrocatalyzed radical coupling reaction was developed. Cyclic aliphatic amines and N‐heteroaromatic compounds were N‐nitrosated and N‐nitrated, respectively, under mild conditions. Control and competition experiments, as well as kinetic studies, demonstrate that N‐nitrosation and N‐nitration involve two different radical reaction pathways involving N+ and N. radicals. Moreover, the electrocatalysis method enables the preferential activation of the N−H bond over the electrode and thus provides high selectivity for specific N atoms. Finally, this strategy exhibits a broad scope and provides a green and straightforward approach to generate useful N‐nitroso/nitro compounds in good yields.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.202000267