Related Experiment Video
Updated: Jul 12, 2026

Light-driven Enzymatic Decarboxylation
Published on: May 22, 2016
PCET-Enabled Decarboxylative Oxygenation Promoted by Photoexcited Nitroarenes
Alana D Duke1, Subhrashis Banerjee2, Akshata P Thupili1
1Department of Chemistry, New York University, New York, New York 10003, United States.
None:
The valorization of feedstock chemicals is a central objective of synthetic chemistry. We report that tuning the aromatic substituents of photoexcited nitroarenes enables selective decarboxylative oxygenation of carboxylic acids via proton-coupled electron transfer (PCET). The direct engagement of carboxylic acids constitutes a new reactivity for photoexcited nitroarenes, which are known to act as potent and selective HAT agents for thermodynamically accessible, hydridic C-H bonds. The mechanistic details of the transformation were elucidated through experimental and theoretical studies that support both stepwise and concerted PCET-type mechanisms dependent on the oxidation potentials of substrates. The selectivity reported herein for PCET reactivity with O-H bonds in the presence of weaker C-H bonds reveals the tunability of photoexcited nitroarene reagents, as well as their utility in transformations involving the single-electron activation of thermodynamically challenging heteroatom-H bonds.
More Related Videos
Related Concept Videos
Photochemical Electrocyclic Reactions: Stereochemistry
Selection Rules: Photochemical Activation
Thermal and Photochemical Electrocyclic Reactions: Overview
Nitrosation of Enols
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
meta-Directing Deactivators: –NO2, –CN, –CHO, –⁠CO2R, –COR, –CO2H
Cycloaddition Reactions: MO Requirements for Photochemical Activation
![[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
