Murahashi SI, Komiya N, Oda Y, Kuwabara T, Naota T
Department of Chemistry, Graduate School of Engineering Science, Osaka University, 1-3, Machikaneyama, Toyonaka, Osaka 560-8531, Japan.
J Org Chem. 2000 Dec 29;65(26):9186-93. doi: 10.1021/jo001348f.
The ruthenium-catalyzed oxidation of alkanes with tert-butyl hydroperoxide and peracetic acid gives the corresponding ketones and alcohols highly efficiently at room temperature. The former catalytic system, RuCl(2)(PPh(3))(3)-t-BuOOH, is preferable to the oxidation of alkylated arenes to give aryl ketones. The latter system, Ru/C-CH(3)CO(3)H, is suitable especially for the synthesis of ketones and alcohols from alkanes. The ruthenium-catalyzed oxidation of cyclohexane with CH(3)CO(3)H in trifluoroacetic acid/CH(2)Cl(2) at room temperature gave cyclohexyl trifluoroacetate and cyclohexanone with 90% conversion and 90% selectivity (85:15). The mechanistic study indicates that these catalytic oxidations of hydrocarbons involve oxo-ruthenium species as key intermediates.
钌催化的烷烃与叔丁基过氧化氢和过氧乙酸的氧化反应在室温下能高效地生成相应的酮和醇。前一种催化体系RuCl₂(PPh₃)₃ - t-BuOOH，更有利于将烷基化芳烃氧化生成芳基酮。后一种体系Ru/C - CH₃CO₃H，特别适用于由烷烃合成酮和醇。室温下，在三氟乙酸/二氯甲烷中，用CH₃CO₃H对环己烷进行钌催化氧化，得到三氟乙酸环己酯和环己酮，转化率为90%，选择性为90%（85:15）。机理研究表明，这些烃类的催化氧化反应涉及氧钌物种作为关键中间体。
