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Electrochemical Nonacidic N‐Nitrosation/N‐Nitration of Secondary Amines through a Biradical Coupling Reaction
Author(s) -
Zhao JiPing,
Ding Lujia,
Wang PengCheng,
Liu Ying,
Huang MinJun,
Zhou XinLi,
Lu Ming
Publication year - 2020
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.202000267
Subject(s) - nitration , chemistry , nitrosation , nitroso , radical , electrochemistry , nitro , nitroso compounds , photochemistry , medicinal chemistry , combinatorial chemistry , organic chemistry , electrode , alkyl
Abstract An acid‐free N‐nitrosation/nitration of the N−H bonds in secondary amines with Fe(NO 3 ) 3 ⋅ 9H 2 O 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.