Mechanistic Insight into the Photoinduced Decarboxylative Radical Addition of Carboxylic Acid to Alkenes in a Two-Molecule Photoredox System

Toshiki Furutani; Yasunori Matsui; Ryoga Hashimoto; Hiroshi Ikeda; Takuya Ogaki; Mugen Yamawaki; Hirotsugu Suzuki; Yasuharu Yoshimi

doi:10.1021/acs.joc.4c03132

Mechanistic Insight into the Photoinduced Decarboxylative Radical Addition of Carboxylic Acid to Alkenes in a Two-Molecule Photoredox System

J Org Chem. 2025 Mar 21;90(11):4028-4036. doi: 10.1021/acs.joc.4c03132. Epub 2025 Mar 12.

Authors

Toshiki Furutani^{1

2}, Yasunori Matsui^{3

4}, Ryoga Hashimoto¹, Hiroshi Ikeda^{3

4}, Takuya Ogaki^{3

4}, Mugen Yamawaki², Hirotsugu Suzuki¹, Yasuharu Yoshimi¹

Affiliations

¹ Department of Applied Chemistry and Biotechnology, Graduate School of Engineering, University of Fukui, 3-9-1 Bunkyo, Fukui 910-8507, Japan.
² Department of Chemistry and Biology, National Institute of Technology, Fukui College, Geshi-cho, Fukui 916-8507, Japan.
³ Department of Applied Chemistry, Graduate School of Engineering, Osaka Metropolitan University, 1-1 Gakuen-cho, Nakaku, Sakai, Osaka 599-8531, Japan.
⁴ The Research Institute for Molecular Electronic Devices (RIMED), Osaka Metropolitan University, 1-1 Gakuen-cho, Nakaku, Sakai, Osaka 599-8531, Japan.

PMID: 40074669
DOI: 10.1021/acs.joc.4c03132

Abstract

The detailed mechanism of photoinduced decarboxylative radical addition to alkenes using both the effect of an electron donor (ED)/electron acceptor (EA) and laser flash photolysis in a two-molecule photoredox system was investigated. The concentration of EA^•- played an important role in the photoreaction and could be controlled by varying the concentrations of ED/EA and their identity, which influenced ΔG_PET. Higher concentrations of ED/EA and a larger negative ΔG_PET led to a higher concentration of EA^•-, thereby increasing the yield of the adduct; however, the large negative ΔG_PET for the generation of the EDA complex hindered decarboxylation. The two-molecule photoredox system is simple and can be easily tuned by adjusting the concentrations and type (ΔG_PET) of ED/EA through a simple replacement of ED/EA, which is easier than modulating the oxidation/reduction potential in one-molecule photoredox systems.