Nitrene transfer (NT) is a powerful strategy for the direct functionalization of C–H bonds and enables the efficient formation of synthetically valuable C–N bonds under mild conditions. Intramolecular NT reactions are particularly appealing, due to their ability to efficiently construct nitrogen-containing heterocycles, motifs that are prevalent in a wide array of pharmaceuticals and natural products.
The first portion of this talk will highlight our applications of silver-catalyzed NT to the synthesis of diverse N-heterocycles, including compounds with promising activity against Mycobacterium tuberculosis. The second portion of the talk centers on the development and application of a new class of quaternary bis(oxazoline) (QT-BOX) ligands that enable highly site- and enantioselective amidations of benzylic, allylic, and aliphatic C–H bonds. Emphasis will be placed on computational and experimental investigations into the influence of the ligand architecture on reactivity and selectivity. These key findings have inspired diversifications of our initial ligand platforms to expand the scope of stereoselective NT reactions and facilitate functionalizations of challenging unactivated C–H bonds.
