Flavinium Catalysed Photooxidation: Detection and Characterization of Elusive Peroxyflavinium Intermediates
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F19%3A43919765" target="_blank" >RIV/60461373:22310/19:43919765 - isvavai.cz</a>
Result on the web
<a href="https://onlinelibrary.wiley.com/doi/full/10.1002/anie.201906293" target="_blank" >https://onlinelibrary.wiley.com/doi/full/10.1002/anie.201906293</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/anie.201906293" target="_blank" >10.1002/anie.201906293</a>
Alternative languages
Result language
angličtina
Original language name
Flavinium Catalysed Photooxidation: Detection and Characterization of Elusive Peroxyflavinium Intermediates
Original language description
Flavin-based catalysts are photoactive in the visible range which makes them useful in biology and chemistry. Herein, we present electrospray-ionization mass-spectrometry detection of short-lived intermediates in photooxidation of toluene catalysed by flavinium ions (Fl(+)). Previous studies have shown that photoexcited flavins react with aromates by proton-coupled electron transfer (PCET) on the microsecond time scale. For Fl(+), PCET leads to FlH(.+) with the H-atom bound to the N5 position. We show that the reaction continues by coupling between FlH(.+) and hydroperoxy or benzylperoxy radicals at the C4a position of FlH(.+). These results demonstrate that the N5-blocking effect reported for alkylated flavins is also active after PCET in these photocatalytic reactions. Structures of all intermediates were fully characterised by isotopic labelling and by photodissociation spectroscopy. These tools provide a new way to study reaction intermediates in the sub-second time range.
Czech name
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Czech description
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Classification
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
Result continuities
Project
<a href="/en/project/GA18-15175S" target="_blank" >GA18-15175S: Oxidative photocatalytic systems with flavinium salts for direct C-H functionalizations</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2019
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Angewandte Chemie-International Edition
ISSN
1433-7851
e-ISSN
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Volume of the periodical
58
Issue of the periodical within the volume
43
Country of publishing house
DE - GERMANY
Number of pages
9
Pages from-to
15412-15420
UT code for WoS article
000483198600001
EID of the result in the Scopus database
2-s2.0-85071332823