Catalytic Generation of Nitrosocarbonyls Under Mild Conditions: Advances, Challenges, and Opportunities.

catalytic oxidations; nitroso Diels–Alder; nitrosocarbonyl; nitroso‐aldol; nitroso‐ene; Condition; Diels-Alder; Nitroso; Reactive nitrogen; Environmental Chemistry; Chemical Engineering (all); Materials Science (all); Energy (all)

Abstract :

[en] Nitrosocarbonyl species (NOCs), also known as acylnitroso species, are highly reactive nitrogen-containing electrophiles. Since their first reports in the 1970s, they have shown significant synthetic potential for the preparation of aminated substrates. Their widespread adoption as versatile amination reagents began in the 2000s, driven by the development of new organometallic and organocatalytic systems. NOCs are typically generated in situ from stable precursors, such as hydroxamic acids and N-hydroxycarbamates, under oxidative conditions, in the presence of a scavenging substrate. This review highlights recent advances in NOC-based catalytic aminations over the past two decades. Specifically, their catalytic generation using oxygen, reactive oxygen species, and peroxides, followed by a subsequent capture through nitroso Diels-Alder, nitroso-ene, and nitroso-aldol reactions are comprehensively discussed. While most catalytic systems rely on Fe-, Co-, Ni-, Cu-, Mo-, Ru-, and Ir-based catalysts, emerging approaches include organocatalysis, photoredox catalysis, electrochemistry, and enzymatic systems. Sustainability and innovative process technologies are also discussed as future directions.

Research Center/Unit :

MolSys - Molecular Systems - ULiège
Center for Integrated Technology and Organic Synthesis

Disciplines :

Chemistry

Author, co-author :

Tsai, Yi-Hsuan ; Université de Liège - ULiège > Département de chimie (sciences) > Center for Integrated Technology and Organic Synthesis

Campalani, Carlotta ; Université de Liège - ULiège > Département de chimie (sciences) > Center for Integrated Technology and Organic Synthesis

Toupy, Thomas; Center for Integrated Technology and Organic Synthesis (CiTOS), MolSys Research Unit, University of Liège, Liège, Belgium

Jacquemin, Isaline ; Université de Liège - ULiège > Département de chimie (sciences) > Center for Integrated Technology and Organic Synthesis

Monbaliu, Jean-Christophe ; Université de Liège - ULiège > Molecular Systems (MolSys) ; WEL Research Institute, Wavre, Belgique

Language :

English

Title :

Catalytic Generation of Nitrosocarbonyls Under Mild Conditions: Advances, Challenges, and Opportunities.

Publication date :

19 December 2025

Journal title :

ChemSusChem

ISSN :

1864-5631

eISSN :

1864-564X

Publisher :

John Wiley and Sons Inc, Germany

Pages :

e202501565

Peer reviewed :

Peer Reviewed verified by ORBi

Additional URL :

https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/cssc.202501565

Available on ORBi :

since 19 February 2026

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