Introducing 1,3-Enyne Functionalization by Nitrene Transfer Reaction

Anabel M. Rodríguez, Giuseppe Sciortino, Lidia Muñoz-Gutierrez, Francisco Molina, Feliu Maseras, M. Mar Díaz-Requejo, Pedro J. Pérez

Chem. Catalysis 2024, 4, 100865.

https://www.doi.org/10.1016/j.checat.2023.100865  

In the context of carbon-nitrogen bond formation, metal-catalyzed nitrene transfer reactions constitute a powerful transformation. Albeit many saturated and unsaturated substrates can be modified with this strategy, the incorporation of nitrene to enynes yet remains undescribed. Herein we report the first example of this transformation, leading to the formation of propargyl aziridines or to unsaturated sulfinamides, corresponding to the attack of a copper-nitrene intermediate onto the ene or yne sites. DFT studies have provided an explanation to this diverse reactivity, which is sustained on the interactions of the enyne substituent with the pyrazolyl rings of the trispyrazolylborate ancillary ligand of the catalyst.