Oxidations by the system “hydrogen peroxide–manganese(IV) complex–carboxylic acid”: Part 3. Oxygenation of ethane, higher alkanes, alcohols, olefins and sulfides

摘要: The manganese(IV) complex salt [L2Mn2O3](PF6)2 (L = 1,4,7-trimethyl-1,4,7-triazacyclononane) (compound 1, see Scheme 1) very efficiently catalyzes the hydroperoxidation of saturated hydrocarbons, including ethane by H2O2 in acetontitrile or nitromethane solution at low (room lower) temperature, provided a carboxylic (typically acetic) acid is present. tertiary positions disubstituted cyclohexanes proceeds with partial retention configuration acetonitrile solution, while stereoselectivity reaction only negligible acetone solution. system “H2O2–compound 1–MeCO2H” also transforms secondary alcohols into corresponding ketones quantitative yields room temperature within few minutes; aldehydes and acids oxidation primary are lower. Terminal aliphatic olefins such as hexene-1 quantitatively epoxidized same 20 min, epoxide yield analogous styrene attains 60% under conditions. Finally, dimethylsulfide can be selectively converted dimethylsulfoxide 3 h temperature. “tert-BuOOH–compound 1” oxidizes alkanes, addition acetic has less pronounced effect on direction efficiency reaction. Two other checked derivative Mn(IV) (compounds 2 3) well porphyrin Mn(III) 4) exhibited lower activity catalysis alkane tert-BuOOH. © 2001 Elsevier Science B.V. All rights reserved.