# Photosulfoxidation Catalysis as the Driving Principle for Deazaoxaflavin Photoredox Catalyst Formation

**Authors:** Karolína Křížová, Rimeh Ismail, Tung Anh Nguyen, Marek Bříza, Anna O. Geleverya, Chiara Ciotta, Valentino L. P. Guerra, Petr Kovaříček

PMC · DOI: 10.1021/acs.joc.5c00185 · 2025-09-25

## TL;DR

This paper introduces a self-forming photoredox catalyst system based on deazaoxaflavins, which can adapt and improve sustainability in chemical reactions.

## Contribution

A novel, thermodynamically driven method for autonomously forming adaptable photoredox catalysts from deazaoxaflavins.

## Key findings

- Deazaoxaflavins exhibit photocatalytic activity similar to flavins.
- The reversible condensation pathway allows for catalyst adaptability by exchanging components.
- The system can be applied to other photo/organocatalytic reactions under suitable conditions.

## Abstract

Catalysts are essential for sustainability because they
decrease
energy and resource consumption in the production of high value-added
products. The design of a novel catalyst is a challenging and expensive
target, and a simplified methodology for catalyst development can
trigger burgeoning progress in both academic and applied research.
Here, we demonstrate a reaction network that autonomously yields the
photoredox catalyst for the transformation of the provided substrate
under applied catalytic conditions. The system stems from the reversible
condensation pathway leading to deazaoxaflavins, 2H-chromeno­[2,3-d]­pyrimidine synthetic analogs of
flavins, with which they share photoorganocatalytic activity. We report
on the photocatalytic activity of deazaoxaflavins and their covalent
dynamic behavior. The reversibility principle allows for the exchange
of one of the deazaoxaflavin constituents for a different moiety,
thus leading to adaptability of the catalyst. We argue that the observed
phenomenon is of thermodynamic origin and thus can be applied to other
photo/organocatalytic reactions in which the combination of a suitable
substrate and conditions is the governing principle for catalyst formation.

## Full-text entities

- **Chemicals:** 2H-chromeno[2,3-d]pyrimidine (-), flavins (MESH:D005415)

## Figures

7 figures with captions in the complete paper: https://tomesphere.com/paper/PMC12519482/full.md

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Source: https://tomesphere.com/paper/PMC12519482