Bioinspired intramolecular spirocyclopropanation of quinones as an interrupted photoredox process

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F24%3A10490475" target="_blank" >RIV/00216208:11310/24:10490475 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=PoWvOeQ.W5" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=PoWvOeQ.W5</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d4qo01291g" target="_blank" >10.1039/d4qo01291g</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Bioinspired intramolecular spirocyclopropanation of quinones as an interrupted photoredox process

Popis výsledku v původním jazyce

Intramolecular photoreactions of quinones can be interrupted by proton transfer using small molecules, such as trimethylamine N-oxide. This interruption de-excites the reactive spirocyclopropyl intermediates, the structures of which were for the first time confirmed by isolating them in their neutral form. The mild conditions of this process allow the conversion of a broad spectrum of quinones possessing linear and branched substituents to spirocyclopropanes in a catalytic, diastereoselective, and atom-conserving manner. Density functional theory (DFT) calculations were performed to investigate the possible reaction pathways and the origin of stereoselectivity. The established spirocyclopropanation route might be used to perform unconventional transformations of the side chains of quinones and to provide clues for the co-occurrence of certain natural quinones, hydroquinones, and spirocyclopropanes. Small molecules, such as trimethylamine N-oxide, interrupt intramolecular photoreactions of quinones by proton transfer and allow to convert a variety of quinones to spirocyclopropanes in a catalytic, diastereoselective, and atom-conserving manner.

Název v anglickém jazyce

Bioinspired intramolecular spirocyclopropanation of quinones as an interrupted photoredox process

Popis výsledku anglicky

Intramolecular photoreactions of quinones can be interrupted by proton transfer using small molecules, such as trimethylamine N-oxide. This interruption de-excites the reactive spirocyclopropyl intermediates, the structures of which were for the first time confirmed by isolating them in their neutral form. The mild conditions of this process allow the conversion of a broad spectrum of quinones possessing linear and branched substituents to spirocyclopropanes in a catalytic, diastereoselective, and atom-conserving manner. Density functional theory (DFT) calculations were performed to investigate the possible reaction pathways and the origin of stereoselectivity. The established spirocyclopropanation route might be used to perform unconventional transformations of the side chains of quinones and to provide clues for the co-occurrence of certain natural quinones, hydroquinones, and spirocyclopropanes. Small molecules, such as trimethylamine N-oxide, interrupt intramolecular photoreactions of quinones by proton transfer and allow to convert a variety of quinones to spirocyclopropanes in a catalytic, diastereoselective, and atom-conserving manner.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GF21-39639L" target="_blank" >GF21-39639L: Syntéza funkčních materiálů katalytickými cyklotrimerizačními a C-C/C-H funkcionalizačními reakcemi</a><br>

Návaznosti

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

Rok uplatnění

2024

Kód důvěrnosti údajů

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

Název periodika

Organic Chemistry Frontiers

ISSN

2052-4110

e-ISSN

2052-4129

Svazek periodika

11

Číslo periodika v rámci svazku

20

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

9

Strana od-do

5703-5711

Kód UT WoS článku

001298286600001

EID výsledku v databázi Scopus

2-s2.0-85202487305