Efficient ruthenium-catalyzed aerobic oxidation of alcohols using a biomimetic coupled catalytic system.
Efficient aerobic oxidation of alcohols was developed via a biomimetic catalytic system. The principle for this aerobic oxidation is reminiscent of biological oxidation of alcohols via the respiratory chain and involves selective electron/proton transfer. A substrate-selective catalyst (ruthenium complex 1) dehydrogenates the alcohol, and the hydrogens abstracted are transferred to an electron-rich quinone (4b). The hydroquinone thus formed is continuously reoxidized by air with the aid of an oxygen-activating Co[bond]salen type complex (6). Most alcohols are oxidized to ketones in high yield and selectivity within 1-2 h, and the catalytic system tolerates a wide range of O(2) concentrations without being deactivated. Compared to other ruthenium-catalyzed aerobic oxidations this new catalytic system has high turnover frequency (TOF).
Csjernyik
Gábor
G
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-106 91 Stockholm Sweden.
Ell
Alida H
AH
Fadini
Luca
L
Pugin
Benoit
B
Bäckvall
Jan-E
JE
D000332:Aerobiosis; D000438:Alcohols / Q000138:chemical synthesis / Q000737:chemistry; D002384:Catalysis; D006873:Hydroquinones / Q000737:chemistry; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D012428:Ruthenium / Q000737:chemistry*; D013113:Spin Labels; D013379:Substrate Specificity; D013997:Time Factors
D000438:Alcohols; D006873:Hydroquinones; D007659:Ketones; D009942:Organometallic Compounds; D013113:Spin Labels; D012428:Ruthenium