Excited‐State Antiaromaticity Relief‐Guided Discovery of 7‐Hydroxycoumarins as Photoacid Catalysts
Year: 2026
Type: article
Abstract: ABSTRACT Although photoacids have attracted considerable interest for their potential technological and biomedical applications in functional dynamic systems and in phototherapy and biosensing, their application as photocatalysts for synthetic purposes is underexplored. To expand the toolbox of photoacids for organic synthetic applications, we investigate an innovative approach for the identification of photocatalysts among the family of coumarin natural products. Our workflow involves as the initial step, the computational study of the excited‐state antiaromaticity relief of a set of compounds based on the natural product umbelliferone (7‐hydroxycoumarin). Then, compounds exhibiting high antiaromaticity relief guided the selection of potential photoacid catalysts for experimental studies in acetalization reaction. Such an approach led to unraveling three 4‐substituted umbelliferone derivatives, namely 4‐methyl, 4‐trifluoromethyl and 4‐phenyl, as efficient photocatalysts for light‐mediated acetalization, confirming that our workflow may indeed facilitate the discovery of new photoacids suitable for synthetic applications. DFT calculations on the mechanism further support the proposed mode of photoacid reactivity.
Source: ChemCatChem
DOI: 10.1002/cctc.71065
Authors: E. Alexandros Routsi, Maria A. Theodoropoulou, Christiana Mantzourani, Demeter Tzeli, Christoforos G. Kokotos, George Kokotos
Language: English
Subfield: Physical and Theoretical Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W7212440884