Deazaflavin reductive photocatalysis involves excited semiquinone radicals

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F20%3A43920649" target="_blank" >RIV/60461373:22310/20:43920649 - isvavai.cz</a>
Result on the web
<a href="https://www.nature.com/articles/s41467-020-16909-y" target="_blank" >https://www.nature.com/articles/s41467-020-16909-y</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1038/s41467-020-16909-y" target="_blank" >10.1038/s41467-020-16909-y</a>

Result language
angličtina
Original language name
Deazaflavin reductive photocatalysis involves excited semiquinone radicals
Original language description
Flavin-mediated photocatalytic oxidations are established in synthetic chemistry. In contrast, their use in reductive chemistry is rare. Deazaflavins with a much lower reduction potential are even better suited for reductive chemistry rendering also deazaflavin semiquinones as strong reductants. However, no direct evidence exists for the involvement of these radical species in reductive processes. Here, we synthesise deazaflavins with different substituents at C5 and demonstrate their photocatalytic activity in the dehalogenation of p-halogenanisoles with best performance under basic conditions. Mechanistic investigations reveal a consecutive photo-induced electron transfer via the semiquinone form of the deazaflavin as part of a triplet-correlated radical pair after electron transfer from a sacrificial electron donor to the triplet state. A second electron transfer from the excited semiquinone to p-halogenanisoles triggers the final product formation. This study provides first evidence that the reductive power of excited deazaflavin semiquinones can be used in photocatalytic reductive chemistry. © 2020, The Author(s).
Czech name
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Czech description
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Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10401 - Organic chemistry

Project
<a href="/en/project/GA19-09064S" target="_blank" >GA19-09064S: Organic photoredox catalysis in reductive transformations: new area for flavin derivatives</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year
2020
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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