Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 88, Issue 10, Pages 6454-6464Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.2c02952
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In this study, we developed a novel photocarboxylation method using an organic photoredox catalyst and different dihydropyridine compounds in combination with an organic base. Through mechanistic investigations, we discovered the key role of a hydrogen bonding complex between the dihydropyridine and the base. This method allowed for the synthesis of carboxylic acids under mild reaction conditions, with good yields and synthetic versatility.
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.
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