New publication in Angew. Chem. Int. Ed. about Cu nitrenes online

The discovery of terminal copper nitrenes led us to find a long-missing link in the family of copper nitrenes. They have been predicted by theory and are pursued since decades. Their remarkable reactivity in terms of direct C–H-aminations of unsaturated C–H-compounds is direcetly linked to the existance of terminal copper nitrenes. The term terminal simply describes the occurrance of an end-on bound nitrene fragment to the copper centre.

To date, only a few copper nitrenes are reported, but neither a terminal species or monometallic species was found. Our low-temperature stabilised nitrenes are based on bis(pyrazolyl)methane ligands and have been directly observed by Cryo-ESI mass spectrometry and UV/Vis spectroscopy. Their reactivity in stoichiometric reactions was followed by UV/Vis spectroscopy. In the end, a catalytic protocol was discovered, leading to the C–H-Amination of cyclohexane and toluene, compounds with very strong C–H bonds.

This research will stimulate further efforts for the atom-efficient synthesis of organic compounds and helps to better understand the optimisation of crucial components in C–H insertions.

The article Designed to react: Terminal Copper Nitrenes and their Application in Catalytic C-H Aminations is available on the webpage of the publisher.