Ruthenium-Catalyzed Oxidation of Alkenes, Alkynes, and Alcohols to Organic Acids with Aqueous Hydrogen Peroxide

• Published in: Chemistry, an Asian journal an Asian journal, 2006-09, Vol.1 (3), p.453-458
• Main Authors: Che, Chi-Ming, Yip, Wing-Ping, Yu, Wing-Yiu
• Format: Article
• Language: English
• Subjects: Adipates - chemistry; alcohols; Alcohols - chemistry; alkenes; Alkenes - chemistry; alkynes; Alkynes - chemistry; Carbon - chemistry; Carboxylic Acids - chemistry; Catalysis; Chemistry, Pharmaceutical - methods; Cyclohexenes - chemistry; Hydrogen Peroxide - chemistry; Hydrogen Peroxide - pharmacology; Models, Chemical; Oxidants - chemistry; oxidation; Oxygen - chemistry; Oxygen - metabolism; ruthenium; Ruthenium - pharmacology
• ISSN: 1861-4728; 1861-471X
• DOI: 10.1002/asia.200600091

A protocol that adopts aqueous hydrogen peroxide as a terminal oxidant and [(Me3tacn)(CF3CO2)2RuIII(OH2)]CF3CO2 (1; Me3tacn=1,4,7‐trimethyl‐1,4,7‐triazacyclononane) as a catalyst for oxidation of alkenes, alkynes, and alcohols to organic acids in over 80 % yield is presented. For the oxidation of cyclohexene to adipic acid, the loading of 1 can be lowered to 0.1 mol %. On the one‐mole scale, the oxidation of cyclohexene, cyclooctene, and 1‐octanol with 1 mol % of 1 produced adipic acid (124 g, 85 % yield), suberic acid (158 g, 91 % yield), and 1‐octanoic acid (129 g, 90 % yield), respectively. The oxidative CC bond‐cleavage reaction proceeded through the formation of cis‐ and trans‐diol intermediates, which were further oxidized to carboxylic acids via CC bond cleavage. Ru‐dy to the rescue! Alkenes, alkynes, and alcohols can be oxidized by H2O2 to the corresponding carboxylic acids with the help of a RuIII catalyst (example shown; Me3tacn=1,4,7‐trimethyl‐1,4,7‐triazacyclononane). This one‐pot reaction can be scaled up for industrial applications.