Base Metal Catalysis in Nitrene Transfer Reactions

Leveraging base metal catalysis to transform small organic molecules by forging X-N bonds (X = C, N, P, S) through nitrene transfer reactions (NTRs) renders a robust and sustainable paradigm shift for preparing valuable amine building blocks. Over the last four decades, 3d metal-catalyzed NTRs have received significant attention in the field of organic synthesis. This review will thoroughly discuss the manipulation of various complexes of base metals, such as Mn, Fe, Co, Ni, and Cu, to control the reaction pathways for X-N bond formation using different nitrene precursors. This review will encompass exemplary, pioneering, and pertinent synthesis in this area and will comprehensively elucidate the mechanistic rationale behind each 3d metals. The reactivity, regioselectivity, chemoselectivity and enantioselectivity of those novel base-metal catalysts are an inevitable part of this discussion. We will also address the inherent limitations and potential opportunities within this specific field of study.