Electron-Deficient Alloxazinium Salts: Efficient Organocatalysts of Mild and Chemoselective Sulfoxidations with Hydrogen Peroxide

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F13%3A00399703" target="_blank" >RIV/61388955:_____/13:00399703 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/60461373:22310/13:43896597 RIV/60461373:22810/13:43896597

Výsledek na webu

<a href="http://dx.doi.org/10.1002/adsc.201300617" target="_blank" >http://dx.doi.org/10.1002/adsc.201300617</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/adsc.201300617" target="_blank" >10.1002/adsc.201300617</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Electron-Deficient Alloxazinium Salts: Efficient Organocatalysts of Mild and Chemoselective Sulfoxidations with Hydrogen Peroxide

Popis výsledku v původním jazyce

A series of substituted alloxazinium perchlorates has been prepared and tested as catalysts for the oxidation of sulfides to sulfoxides with hydrogen peroxide. The logarithms of the observed rate constants of thioanisole oxidation correlate with the Hammett ? constants of the substituents on the alloxazinium catalysts, as well as with their reduction potentials E0 and their pKR+ values, representing the alloxazinium salt/pseudobase equilibrium. The stronger the electron-withdrawing substituent, the moreefficient is the alloxazinium catalyst. The alloxazinium salts with a cyano or trifluoromethyl group in position 8 proved to be the most efficient, operating at room temperature at small loadings, down to 0.1?mol%, achieving turnover number values of upto 640 and acceleration by a factor of 350 relative to the non-catalyzed oxidation. The 8-cyanoalloxazinium perchlorate was evaluated as the best catalyst; however, due to its relatively good accessibility, the 8-(trifluoromethyl)alloxaz

Název v anglickém jazyce

Electron-Deficient Alloxazinium Salts: Efficient Organocatalysts of Mild and Chemoselective Sulfoxidations with Hydrogen Peroxide

Popis výsledku anglicky

A series of substituted alloxazinium perchlorates has been prepared and tested as catalysts for the oxidation of sulfides to sulfoxides with hydrogen peroxide. The logarithms of the observed rate constants of thioanisole oxidation correlate with the Hammett ? constants of the substituents on the alloxazinium catalysts, as well as with their reduction potentials E0 and their pKR+ values, representing the alloxazinium salt/pseudobase equilibrium. The stronger the electron-withdrawing substituent, the moreefficient is the alloxazinium catalyst. The alloxazinium salts with a cyano or trifluoromethyl group in position 8 proved to be the most efficient, operating at room temperature at small loadings, down to 0.1?mol%, achieving turnover number values of upto 640 and acceleration by a factor of 350 relative to the non-catalyzed oxidation. The 8-cyanoalloxazinium perchlorate was evaluated as the best catalyst; however, due to its relatively good accessibility, the 8-(trifluoromethyl)alloxaz

Druh

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

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

<a href="/cs/project/GAP207%2F12%2F0447" target="_blank" >GAP207/12/0447: Organokatalytické stereoselektivní oxidace s využitím heterocyklických hydroperoxidů</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2013

Kód důvěrnosti údajů

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

Název periodika

Advanced Synthesis & Catalysis

ISSN

1615-4150

e-ISSN

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Svazek periodika

355

Číslo periodika v rámci svazku

17

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

12

Strana od-do

3451-3462

Kód UT WoS článku

000327984000020

EID výsledku v databázi Scopus

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