[en] Dinitrogen trioxide (N2 O3 ) is a powerful and efficient nitrosating agent that comes with an unprecedented atom economy. However, the synthetic application of N2 O3 is still underdeveloped mostly due to its inherent instability and the lack of reliable protocols for its preparation. This paper presents an open-source setup and procedure for the on-demand generation of anhydrous N2 O3 solution (up to 1 M), which can be further used for reactions under batch and flow conditions. The accuracy and stability of N2 O3 concentration are guaranteed with the absence of head-space in the setup and with the synchronization of the gas flows. The reliability of this protocol is demonstrated by >30 worked examples in the nitrosative synthesis of heterocycles-a library of structurally diverse benzotriazoles and sydnones. Kinetic and mechanistic aspects of the N-nitrosative steps are also explored.
Disciplines :
Chemistry
Author, co-author :
Chen, Yuesu ; Université de Liège - ULiège > Molecular Systems (MolSys)
Renson, Sébastien ; Center for Integrated Technology and Organic Synthesis (CiTOS), MolSys Research Unit, University of Liège, B6a, Room 3/19, Allée du Six Août 13, 4000, Liège, Sart Tilman, Belgium
F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE]
Funding text :
This work was supported by the “Fonds de la Recherche Scientifique de Belgique (F.R.S.‐FNRS)” (Incentive grant for scientific research MIS under grant No F453020F, JCMM). Computational resources were provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the F.R.S.‐FNRS under Grant No. 2.5020.11 and by the Walloon Region.
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