Direct Activation of the C(sp3)-NH2 Bond of Primary Aliphatic Alkylamines by a High-Valent CoIII,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 CoIII,IV2(mu-O)2 diamond core complex. This reaction results in the installation of other functional groups such as halides and alkenes onto the alpha-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.

Automated summary

In this work, a novel method to activate the C(sp3)-NH2 bond of primary alkylamines using a high-valent dinuclear CoIII,IV2(mu-O)2 diamond core complex was discovered. This reaction allows for the installation of functional groups onto the alpha-carbon center while oxidizing the nitrogen atom on the amino group to form NH2OH. These findings provide insights for future versatile functionalization of primary alkylamines based on the dinuclear cobalt system.