On Demand Flow Platform for the Generation of Anhydrous Dinitrogen Trioxide and Its Further Use in<i>N</i>‐Nitrosative Reactions
Yuesu Chen, Sébastien Renson, Jean‐Christophe M. Monbaliu
Abstract
Abstract Dinitrogen trioxide (N 2 O 3 ) is a powerful and efficient nitrosating agent that comes with an unprecedented atom economy. However, the synthetic application of N 2 O 3 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 N 2 O 3 solution (up to 1 M), which can be further used for reactions under batch and flow conditions. The accuracy and stability of N 2 O 3 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.