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

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GA19-09064S" target="_blank" >GA19-09064S: Organická fotoredoxní katalýza v redukčních transformacích: nový prostor pro deriváty flavinů</a><br>

Návaznosti

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

Rok uplatnění

2022

Kód důvěrnosti údajů

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

Název periodika

Chemistry A European Journal

ISSN

0947-6539

e-ISSN

—

Svazek periodika

28

Číslo periodika v rámci svazku

46

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

12

Strana od-do

nestrankovano

Kód UT WoS článku

000815354500001

EID výsledku v databázi Scopus

2-s2.0-85132553017