Mechanisms of orthogonal photodecarbonylation reactions of 3-hydroxyflavone-based acid-base forms

0523607 - ÚOCHB 2021 RIV US eng J - Journal Article
Russo, M. - Štacko, P. - Nachtigallová, Dana - Klán, P.
Mechanisms of orthogonal photodecarbonylation reactions of 3-hydroxyflavone-based acid-base forms.
Journal of Organic Chemistry. Roč. 85, č. 5 (2020), s. 3527-3537. ISSN 0022-3263. E-ISSN 1520-6904
Institutional support: RVO:61388963
Keywords : intramolecular proton transfer * Gaussian basis sets * carbon monoxide
OECD category: Physical chemistry
Impact factor: 4.354, year: 2020
Method of publishing: Limited access
https://pubs.acs.org/doi/10.1021/acs.joc.9b03248

Carbon monoxide is a naturally occurring gasotransmitter combining inherent toxicity with a remarkable therapeutic potential and arduous administration. Photoactivatable carbon monoxide-releasing molecules (photoCORMs) are chemical agents that allow for precise spatial and temporal control over the CO release. In this work, we present a comprehensive mechanistic study of the photochemical CO release from 3-hydroxy-2-phenyl-4H-chromen-4-one, a π-extended 3-hydroxyflavone photoCORM, in methanol using steady-state and transient absorption spectroscopies and quantum chemical calculations. The multiplicity of the productive excited states and the role of oxygen (O2) in the CO production are emphasized, revealing a photoreaction dichotomy of the 3-hydroxyflavone acid and base forms. The utilization of three major orthogonal mechanistic pathways, all of which lead to the CO release, can fuel future endeavors to improve the CO release efficacy of 3-hydroxyflavone-based derivatives and refine their potential medical applications as photoCORMs.
Permanent Link: http://hdl.handle.net/11104/0307931