Efficient metal-free aerobic photooxidation of sulfides to sulfoxides mediated by a vitamin B2 derivative and visible light

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22810%2F16%3A43902793" target="_blank" >RIV/60461373:22810/16:43902793 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/60461373:22310/16:43902793

Výsledek na webu

<a href="http://dx.doi.org/10.1002/adsc.201501123" target="_blank" >http://dx.doi.org/10.1002/adsc.201501123</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/adsc.201501123" target="_blank" >10.1002/adsc.201501123</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Efficient metal-free aerobic photooxidation of sulfides to sulfoxides mediated by a vitamin B2 derivative and visible light

Popis výsledku v původním jazyce

We developed a metal-free process for the aerobic photooxygenation of sulfides to sulfoxides mediated by riboflavin tetraacetate or riboflavin (vitamin B2) photocatalysts and visible light (455 nm) in acetonitrile-water (85:15 v/v) mixture. The optimised solvent system leads to both singlet-oxygen and electron-transfer pathways in photooxygenation, thus allowing oxidation of electron-poor and electron-rich thioanisoles, dialkyl sulfides and sterically hindered sulfides. Besides having a broad substrate scope, the method has very short reaction times and requires low catalyst loading (down to 0.1 mol%). These properties are due to the high photocatalyst stability and the extremely high quantum yields (1.3 for thioanisole oxygenation). Moreover, the method is chemoselective, producing only sulfoxides without over-oxidation to sulfones. Taking into account broad substrate scope, high selectivity and high efficiency, this method distinguishes itself from those previously reported. Other advantages include easy work-up of the reaction mixture, the availability and biodegradability of the photocatalysts and mild reaction conditions. We demonstrated, on a preparative scale, its practical application in the synthesis of the psychostimulant modafinil, in the selective oxidation of methionine derivatives, and in the detoxification of mustard gas.

Název v anglickém jazyce

Efficient metal-free aerobic photooxidation of sulfides to sulfoxides mediated by a vitamin B2 derivative and visible light

Popis výsledku anglicky

We developed a metal-free process for the aerobic photooxygenation of sulfides to sulfoxides mediated by riboflavin tetraacetate or riboflavin (vitamin B2) photocatalysts and visible light (455 nm) in acetonitrile-water (85:15 v/v) mixture. The optimised solvent system leads to both singlet-oxygen and electron-transfer pathways in photooxygenation, thus allowing oxidation of electron-poor and electron-rich thioanisoles, dialkyl sulfides and sterically hindered sulfides. Besides having a broad substrate scope, the method has very short reaction times and requires low catalyst loading (down to 0.1 mol%). These properties are due to the high photocatalyst stability and the extremely high quantum yields (1.3 for thioanisole oxygenation). Moreover, the method is chemoselective, producing only sulfoxides without over-oxidation to sulfones. Taking into account broad substrate scope, high selectivity and high efficiency, this method distinguishes itself from those previously reported. Other advantages include easy work-up of the reaction mixture, the availability and biodegradability of the photocatalysts and mild reaction conditions. We demonstrated, on a preparative scale, its practical application in the synthesis of the psychostimulant modafinil, in the selective oxidation of methionine derivatives, and in the detoxification of mustard gas.

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/GA14-09190S" target="_blank" >GA14-09190S: Fotoorganokatalytická metateze: [2+2] cykloadice alkenů a štěpení cyklobutanového kruhu s využitím flavinů a viditelného světla</a><br>

Návaznosti

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

Rok uplatnění

2016

Kód důvěrnosti údajů

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

Název periodika

ADVANCED SYNTHESIS &amp; CATALYSIS

ISSN

1615-4150

e-ISSN

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Svazek periodika

358

Číslo periodika v rámci svazku

10

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

10

Strana od-do

"1654?1663"

Kód UT WoS článku

000377268100015

EID výsledku v databázi Scopus

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