Visible light photocatalytic reduction of aldehydes by Rh(III)-H: a detailed mechanistic study

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14310%2F15%3A00087028" target="_blank" >RIV/00216224:14310/15:00087028 - isvavai.cz</a>

Výsledek na webu

<a href="http://pubs.rsc.org/en/Content/ArticleLanding/2015/SC/C4SC03709J#!divAbstract" target="_blank" >http://pubs.rsc.org/en/Content/ArticleLanding/2015/SC/C4SC03709J#!divAbstract</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c4sc03709j" target="_blank" >10.1039/c4sc03709j</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Visible light photocatalytic reduction of aldehydes by Rh(III)-H: a detailed mechanistic study

Popis výsledku v původním jazyce

The chemoselective photoreduction of aldehydes in the presence of ketones was achieved using triethanolamine (TEOA) as sacrificial electron donor, proflavine (PF) as photocatalyst and [Cp*Rh(III)(bpy) Cl]Cl (Rh-cat) as mediator. The reducing agent, whichreacts with the carbonyl group was found to be [Cp*Rh(III)(bpy)H]Cl (Rh(III)-H). Contrary to formate-based reduction, its slow photochemical in situ generation enables to kinetically distinguish aldehydes from ketones. The inherent reactivity differenceof the carbonyl compounds is transferred by the method into synthetically useful reaction selectivities. The substrate scope is broad with excellent yields. A detailed study of the reaction mechanism reveals that the photoreduction of the PF triplet andthe subsequent reduction of the Rh-cat leading to Rh(III)-H represents the major reaction pathway, which is highly oxygen sensitive.

Název v anglickém jazyce

Visible light photocatalytic reduction of aldehydes by Rh(III)-H: a detailed mechanistic study

Popis výsledku anglicky

The chemoselective photoreduction of aldehydes in the presence of ketones was achieved using triethanolamine (TEOA) as sacrificial electron donor, proflavine (PF) as photocatalyst and [Cp*Rh(III)(bpy) Cl]Cl (Rh-cat) as mediator. The reducing agent, whichreacts with the carbonyl group was found to be [Cp*Rh(III)(bpy)H]Cl (Rh(III)-H). Contrary to formate-based reduction, its slow photochemical in situ generation enables to kinetically distinguish aldehydes from ketones. The inherent reactivity differenceof the carbonyl compounds is transferred by the method into synthetically useful reaction selectivities. The substrate scope is broad with excellent yields. A detailed study of the reaction mechanism reveals that the photoreduction of the PF triplet andthe subsequent reduction of the Rh-cat leading to Rh(III)-H represents the major reaction pathway, which is highly oxygen sensitive.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CC - Organická chemie

OECD FORD obor

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Projekt

<a href="/cs/project/LO1214" target="_blank" >LO1214: Centrum pro výzkum toxických látek v prostředí</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2015

Kód důvěrnosti údajů

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

Název periodika

CHEMICAL SCIENCE

ISSN

2041-6520

e-ISSN

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Svazek periodika

6

Číslo periodika v rámci svazku

3

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

8

Strana od-do

2027-2034

Kód UT WoS článku

000349832600055

EID výsledku v databázi Scopus

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