Direct Activation of the C(sp³)-NH₂ Bond of Primary Aliphatic Alkylamines by a High-Valent Co^III,IV₂(μ-O)₂ Diamond Core Complex

Aliphatic alkylamines are abundant feedstock and versatile building blocks for many organic transformations. While remarkable progress has been made to construct C-N bonds on aliphatic and aromatic carbon centers, the activation and functionalization of C(sp³)-NH₂ bonds in primary alkylamines remain a challenging process. In the present work, we discovered an unprecedented method to directly activate the C(sp³)-NH₂ bond of primary alkylamines by a high-valent dinuclear Co^III,IV₂(μ-O)₂ diamond core complex. This reaction results in the installation of other functional groups such as halides and alkenes onto the α-carbon center concomitant with the 2-e^- oxidation of the nitrogen atom on the amino group to form NH₂OH. These results shed light on future development enabling versatile functionalization of primary alkylamines based on the dinuclear cobalt system. Moreover, our work suggests that a related high-valent copper-oxo intermediate is likely generated in the ammonia monooxygenase catalytic cycle to affect the oxidation of NH₃ to NH₂OH.