Ruthenium-catalyzed oxidation of alkenes, alkynes, and alcohols to organic acids with aqueous hydrogen peroxide.
A protocol that adopts aqueous hydrogen peroxide as a terminal oxidant and [(Me3tacn)(CF3CO2)2Ru(III)(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.
Che
Chi-Ming
CM
Department of Chemistry and Open Laboratory of Chemical Biology of the Institute of Molecular Technology for Drug Discovery and Synthesis, The University of Hong Kong, Pokfulam Road, Hong Kong SAR, China. cmche@hku.hk
Yip
Wing-Ping
WP
Yu
Wing-Yiu
WY
D000272:Adipates / Q000737:chemistry; D000438:Alcohols / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry*; D000480:Alkynes / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry; D002384:Catalysis; D002626:Chemistry, Pharmaceutical / Q000379:methods; D053138:Cyclohexenes / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry* / Q000494:pharmacology; D008956:Models, Chemical; D016877:Oxidants / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry / Q000378:metabolism; D012428:Ruthenium / Q000494:pharmacology*
D000272:Adipates; D000438:Alcohols; D000475:Alkenes; D000480:Alkynes; D002264:Carboxylic Acids; D053138:Cyclohexenes; D016877:Oxidants; C052568:cyclohexene; D002244:Carbon; C029900:adipic acid; D012428:Ruthenium; D006861:Hydrogen Peroxide; D010100:Oxygen