Research Projects

The formation of C-N bonds is a significant research area in catalysis, particularly in pharmaceuticals. Synthetic chemists are constantly seeking novel strategies to forge C-N bonds in a step, atom, and redox-economic way. Oxidative Radical Polar Crossover (ORPC) assisted photo-redox catalysis is a highly attractive approach for one-pot transformations, satisfying both radical and polar reactivity. Merging this radical ORPC process with the well-explored Metal Hydride Hydrogen Atom Transfer (MHAT) could empower a radical process that could tackle many existing unsolved problems in organic synthesis. This proposal proposes two novel strategies for the synthesis of amine under sustainable photocatalysis conditions: redox-neutral photochemical construction of C-N bonds from aliphatic carboxylic acids via ORPC and Markovnikov photocatalytic hydroamination of unactivated alkenes by merging with MHAT catalysis. The proposed strategy aims to be environmentally sustainable and minimize waste production. Strategy 1 involves a redox-neutral synthesis of aliphatic amines from carboxylic acids, which is reduced to an alkyl radical via a photoredox-catalyzed single electron transfer process. The radical undergoes ORPC and converts to a carbocation, followed by a Ritter-type reaction with nitriles that yields amines. Strategy 2 focuses on a Markovnikov hydroamination of unactivated alkenes using triple cobalt/photo-redox/proton donor catalysis. This approach allows for more precise control of protons and electrons, offering a unique approach to the hydroamination of unactivated alkenes.