Abstract:
The development of methods for the selective formation of C–N bonds remains a challenge in catalysis, particularly catalysts that are able to accommodate both simple hydrocarbon feedstocks and complex bioactive platforms. Our group leverages the distinctive and varied coordination environments available to silver(I) complexes to develop a uniquely versatile and tunable platform for addressing challenges in chemo-, site- and stereoselective C–H amidation reactions via nitrene transfer.
A hallmark of our work is the careful modulation of the ligand environment and nitrene precursor to achieve levels of selectivity difficult to access using traditional catalysts for group transfer. Selectivity can be achieved in diverse reactions that include chemoselective, asymmetric aziridination, site-selective amidations of diverse C–H bonds] dearomative amidations and skeletal rearrangements. Recent advances highlight the power of our platform in enabling non-directed, intermolecular C–H functionalizations under mild conditions, expanding substrate scope to include complex arenes, heterocycles, and bioactive scaffolds. In addition, nitrene transfer can be telescoped with carbene transfer to streamline the syntheses of nitrogen-containing heterocycles that are important to medicinal chemistry, agrochemicals, materials science and beyond.