Chemoselective Anaerobic Dehydrogenation of Alcohols by Using Visible Light and a Positively Charged Deazaflavin Catalyst Regenerated by Acetonitrile Solvent

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F25%3A00605119" target="_blank" >RIV/61388963:_____/25:00605119 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/60461373:22310/25:43931153 RIV/60461373:22810/25:43931153

Výsledek na webu

<a href="https://doi.org/10.1002/cctc.202401795" target="_blank" >https://doi.org/10.1002/cctc.202401795</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/cctc.202401795" target="_blank" >10.1002/cctc.202401795</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Chemoselective Anaerobic Dehydrogenation of Alcohols by Using Visible Light and a Positively Charged Deazaflavin Catalyst Regenerated by Acetonitrile Solvent

Popis výsledku v původním jazyce

Three series of novel deazaflavinum salts differing in their substitutions at positions 5 (R = H, phenyl, or mesityl), 7, and 8 (R = OMe, Me, H, or Cl) were synthesized as potential catalysts of a novel chemoselective visible light-mediated anaerobic oxidation of primary and secondary alcohols to carbonyl compounds. This mild procedure uses acetonitrile as a solvent, which acts simultaneously as a sacrificial electron acceptor (in place of the oxygen usually used in photooxidation reactions), and therefore the reaction does not need any additives. Structure and properties-versus-catalytic activity studies identified 5-mesityl-7,8-dimethoxy-3-methyldeazaflavinium chloride (3a-Cl) as the most potent catalyst. 3a-Cl was effective in non-deuterated acetonitrile (CH3CN), unlike its original 5-phenyl analogue 2a-Cl, which is efficient only in deuterated solvent (CD3CN). This difference arises because the regeneration of the 2a-Cl catalyst is slower in CH3CN than in CD3CN. Our method using the optimized 3a-Cl photocatalyst and CH3CN as a sacrificial oxidant and solvent in one is a useful addition to synthetic organic chemistry. Anaerobic conditions prevent side oxygenation reactions and overoxidations that usually occur in air or oxygen. This property makes this method suitable for dehydrogenations of alcohols that possess additional group(s) sensitive to oxygenation.

Název v anglickém jazyce

Chemoselective Anaerobic Dehydrogenation of Alcohols by Using Visible Light and a Positively Charged Deazaflavin Catalyst Regenerated by Acetonitrile Solvent

Popis výsledku anglicky

Three series of novel deazaflavinum salts differing in their substitutions at positions 5 (R = H, phenyl, or mesityl), 7, and 8 (R = OMe, Me, H, or Cl) were synthesized as potential catalysts of a novel chemoselective visible light-mediated anaerobic oxidation of primary and secondary alcohols to carbonyl compounds. This mild procedure uses acetonitrile as a solvent, which acts simultaneously as a sacrificial electron acceptor (in place of the oxygen usually used in photooxidation reactions), and therefore the reaction does not need any additives. Structure and properties-versus-catalytic activity studies identified 5-mesityl-7,8-dimethoxy-3-methyldeazaflavinium chloride (3a-Cl) as the most potent catalyst. 3a-Cl was effective in non-deuterated acetonitrile (CH3CN), unlike its original 5-phenyl analogue 2a-Cl, which is efficient only in deuterated solvent (CD3CN). This difference arises because the regeneration of the 2a-Cl catalyst is slower in CH3CN than in CD3CN. Our method using the optimized 3a-Cl photocatalyst and CH3CN as a sacrificial oxidant and solvent in one is a useful addition to synthetic organic chemistry. Anaerobic conditions prevent side oxygenation reactions and overoxidations that usually occur in air or oxygen. This property makes this method suitable for dehydrogenations of alcohols that possess additional group(s) sensitive to oxygenation.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GA23-06465S" target="_blank" >GA23-06465S: Spojení fotochemie a elektrochemie v redoxní katalýze na bázi flavinů</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

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

Název periodika

ChemCatChem

ISSN

1867-3880

e-ISSN

1867-3899

Svazek periodika

17

Číslo periodika v rámci svazku

5

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

8

Strana od-do

e202401795

Kód UT WoS článku

001384365400001

EID výsledku v databázi Scopus

2-s2.0-86000387895