In this lecture, I will discuss recent developments from our lab in the area of transition metal catalyzed C-H activation to afford novel C-X funtionalized products. A perspective of the current state of the field will be presented with connections to key conceptual advances regarding the preparation and characterization of high-valent metal-oxo and metal-hydroxo species and their reactivity. The main focus will include manganese and iron species that perform radical mediated heteroatom rebound catalysis. We have directly observed and kinetically characterized the reactive Mn=O and Mn-OH intermediates both in synthetic and biomimetic systems. Early studies of C-H hydroxylation led to the discovery of a selective and efficient C-H fluorination mediated by model manganese porphyrins and, most recently, extension to C-H azidation and isocyanation. The methods allow facile production of fluorinated and nitrogenated building blocks and drug analogs directly from simple starting materials. The processes are robust and are tolerant of air and moisture allowing for simple bench-top operations and extension to multi-well plates for high throughput screening. Further, fluorination with 18F sources are found to be particularly efficient, allowing access to new PET imaging agents.

Iron and manganese mediated heteroatom rebound catalysis

256th National Meeting (2018)

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