Direct Activation of the C(sp)-NH Bond of Primary Aliphatic Alkylamines by a High-Valent Co(μ-O) 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(sp)-NH bonds in primary alkylamines remain a challenging process. In the present work, we discovered an unprecedented method to directly activate the C(sp)-NH bond of primary alkylamines by a high-valent dinuclear Co(μ-O) 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 NHOH. 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 NH to NHOH.