Tuning Deazaflavins Towards Highly Potent Reducing Photocatalysts Guided by Mechanistic Understanding – Enhancement of the Key Step by the Internal Heavy Atom Effect

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F22%3A43925219" target="_blank" >RIV/60461373:22310/22:43925219 - isvavai.cz</a>
Result on the web
<a href="https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.202200768" target="_blank" >https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.202200768</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/chem.202200768" target="_blank" >10.1002/chem.202200768</a>

Result language
angličtina
Original language name
Tuning Deazaflavins Towards Highly Potent Reducing Photocatalysts Guided by Mechanistic Understanding – Enhancement of the Key Step by the Internal Heavy Atom Effect
Original language description
Deazaflavins are well suited for reductive chemistry acting via a consecutive photo-induced electron transfer, in which their triplet state and semiquinone – the latter is formed from the former after electron transfer from a sacrificial electron donor – are key intermediates. Guided by mechanistic investigations aiming to increase intersystem crossing by the internal heavy atom effect and optimising the concentration conditions to avoid unproductive excited singlet reactions, we synthesised 5-aryldeazaflavins with Br or Cl substituents on different structural positions via a three-component reaction. Bromination of the deazaisoalloxazine core leads to almost 100 % triplet yield but causes photo-instability and enhances unproductive side reactions. Bromine on the 5-phenyl group in ortho position does not affect the photostability, increases the triplet yield, and allows its efficient usage in the photocatalytic dehalogenation of bromo- and chloroarenes with electron-donating methoxy and alkyl groups even under aerobic conditions. Reductive powers comparable to lithium are achieved. © 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.
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
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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
2022
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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