Issue 5, 2022

Mechanistic studies of visible light-induced CO release from a 3-hydroxybenzo[g]quinolone

Abstract

Organic compounds that can be triggered using light to release CO in biological environments are of significant current interest to probe the role of CO in biology and as potential therapeutics. We recently reported that a 3-hydroxybenzo[g]quinolone (5) can be used as a CO delivery molecule to produce anticancer and potent anti-inflammatory effects. Herein we report mechanistic studies of the visible light-induced CO release reaction of this compound. In wet CH3CN under aerobic conditions, 5 releases 0.90(2) equivalents of CO upon illumination with visible light (419 nm) to give a single depside product. Performing the same reaction under an 18O2 atmosphere results in quantitative incorporation of two labeled oxygen atoms in the depside product. Monitoring via 1H NMR and UV-vis during the illumination of 5 in CH3CN using 419 nm light revealed the substoichiometric formation of a diketone (6) in the reaction mixture. H2O2 formation was detected in the same reaction mixtures. DFT studies indicate that upon light absorption an efficient pathway exists for the formation of a triplet excited state species (5b) that can undergo reaction with 3O2 resulting in CO release. DFT investigations also provide insight into diketone (6) and H2O2 formation and subsequent reactivity. The presence of water and exposure to visible light play an important role in lowering activation barriers in the reaction between 6 and H2O2 to give CO. Overall, two reaction pathways have been identified for CO release from a 3-hydroxybenzo[g]quinolone.

Graphical abstract: Mechanistic studies of visible light-induced CO release from a 3-hydroxybenzo[g]quinolone

Supplementary files

Article information

Article type
Paper
Submitted
11 10月 2021
Accepted
27 12月 2021
First published
20 1月 2022
This article is Open Access
Creative Commons BY-NC license

RSC Adv., 2022,12, 2751-2758

Mechanistic studies of visible light-induced CO release from a 3-hydroxybenzo[g]quinolone

M. Popova, T. Borowski, J. G. D. Elsberg, C. T. Dederich and L. M. Berreau, RSC Adv., 2022, 12, 2751 DOI: 10.1039/D1RA07527F

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements