A Proton-Coupled Electron Transfer Strategy to the Redox-Neutral Photocatalytic CO<sub>2</sub> Fixation
Pietro Franceschi, Elena Rossin, Giulio Goti, Angelo Scopano, Alberto Vega‐Peñaloza, Mirco Natali, Deepak Singh, Andrea Sartorel, Luca Dell’Amico
Abstract
Herein, we report our study on the design and development of a novel photocarboxylation method. We have used an organic photoredox catalyst (PC, 4CzIPN) and differently substituted dihydropyridines (DHPs) in combination with an organic base (1,5,7-triazabicyclodec-5-ene, TBD) to access a proton-coupled electron transfer (PCET) based manifold. In depth mechanistic investigations merging experimental analysis (NMR, IR, cyclic voltammetry) and density-functional theory (DFT) calculations reveal the key activity of a H-bonding complex between the DHP and the base. The thermodynamic and kinetic benefits of the PCET mechanism allowed the implementation of a redox-neutral fixation process leading to synthetically relevant carboxylic acids (18 examples with isolated yields up to 75%) under very mild reaction conditions. Finally, diverse product manipulations were performed to demonstrate the synthetic versatility of the obtained products.