Redox strategies to access carbene and nitrene intermediates

Metal carbene and nitrene (radical) transfer catalysis has been employed as an efficient method for the functionalization of C–H, X–H, and C=C bonds. Currently, metal carbene and nitrene intermediates are formed from high energy, pre-functionalized carbene and nitrene precursors. These precursors are often explosive in nature, generate halogenated waste, or lead to a low atom efficient reaction. The latter is caused by functional groups in the precursor that are required for activation, but are not necessary in the desired product. As a result, the direct formation of new bonds is limited to these specific precursors, which consequently limit the applicability of metal carbene and nitrene transfer catalysis.
This dissertation provided insight into the formation of (metal) carbene and nitrene radical intermediates, particularly with the aid of photo- and electrochemistry. Moreover, metal carbene and nitrene radical intermediates were formed from low energy, generally accessible, and bench-stable reagents. These compounds can be viewed as greener carbene and nitrene precursor alternatives. Efforts to improve the catalytic conversion of these compounds, resulting in higher yields, would expand these methods to a broader range of substrates and general applicability.