Flavinium Catalysed Photooxidation: Detection and Characterization of Elusive Peroxyflavinium Intermediates

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Flavinium Catalysed Photooxidation: Detection and Characterization of Elusive Peroxyflavinium Intermediates

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Flavinium Catalysed Photooxidation: Detection and Characterization of Elusive Peroxyflavinium Intermediates

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GA18-15175S" target="_blank" >GA18-15175S: Oxidativní fotokatalytické systémy s flaviniovými solemi pro přímé C-H funkcionalizace</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2019

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Angewandte Chemie-International Edition

ISSN

1433-7851

e-ISSN

—

Svazek periodika

58

Číslo periodika v rámci svazku

43

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

9

Strana od-do

15412-15420

Kód UT WoS článku

000483198600001

EID výsledku v databázi Scopus

2-s2.0-85071332823