Mechanisms of Orthogonal Photodecarbonylation Reactions of 3-Hydroxyflavone-Based Acid-Base Forms
Autoři
RUSSO, Marina (380 Itálie, domácí), Peter ŠTACKO (703 Slovensko, domácí), Dana NACHTIGALLOVÁ (203 Česká republika) a Petr KLÁN (203 Česká republika, garant, domácí)
Vydání
Journal of Organic Chemistry, Washington, D.C. American Chemical Society, 2020, 0022-3263
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 pi-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 (O-2) 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.
Návaznosti
EF17_043/0009632, projekt VaV
Název: CETOCOEN Excellence
GA18-12477S, projekt VaV
Název: Fotoaktivace CO a H2S jako plynných signálních molekul pro biologické a medicinální aplikace
Investor: Grantová agentura ČR, Fotoaktivace CO a H2S jako plynných signálních molekul pro biologické a medicinální aplikace