Research Projects

Organic synthesis is crucial for producing various valuable compounds, but current methods are less efficient and produce large amounts of waste. Developing more efficient synthetic methods could reduce waste and energy use. The decarboxylative coupling of carboxylic acids is a synthetic strategy that involves the removal of a carboxyl group from a carboxylic acid, forming a highly reactive carbon-centered intermediate that can undergo coupling reactions with various nucleophiles. Carboxylic acids are the synthetic equivalents of acyl/aryl/alkyl halides and organometallic reagents. Conventional polar/radical decarboxylation suffers from high temperatures, ortho-substituents, slow rates, and undesirable side reactions. The photoinduced decarboxylation of carboxylic acids is a robust methodology that offers a direct bond formation without the need for prefunctionalization. The ligand lability property of earth-abundant metals can be exploited for the photoinduced formation of the carboxyl radical via a metal carboxylate (RCOO-M(n)Ln). The photoinduced O-M(n) bond homolytic cleavage is owing to a ligand-to-metal-charge transfer (LMCT) and proceeds through a σ(O-M) orbital depopulation or σ*(O-M) orbital population. This unique pathway offers the use of various unactivated carboxylic acids and offers good functional group tolerance and regioselectivity. The proposed project will use aliphatic/aromatic/heteroaromatic carboxylic acids to develop C-N, C-s, C-si, and C-Ge bond formations via photoinduced Ligand-to-Metal Charge Transfer (LMCT) using 3d-transition (Fe, Ni, Cu)/rare-earth (Ce, La) metals.