Efficient ruthenium-catalyzed aerobic oxidation of alcohols using a biomimetic coupled catalytic system
Efficient ruthenium-catalyzed aerobic oxidation of alcohols using a biomimetic coupled catalytic system
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DOI：
10.1021/jo0163750
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发表时间：
2002-03-08
影响因子：
3.6
通讯作者：
Bäckvall, JE
中科院分区：
文献类型：
--
作者：
Csjernyik, G;Éll, AH;Bäckvall, JE
研究了一种高效的仿生催化体系对醇类的好氧氧化。这种需氧氧化的原理让人联想到醇类通过呼吸链的生物氧化，并涉及选择性电子/质子转移。底物选择性催化剂（钌络合物1）使醇脱附，并且所提取的氢被转移到富电子的醌（4 b）。由此形成的对苯二酚借助于氧活化的Co-salen型络合物（6）被空气连续再氧化。大多数醇在1-2小时内以高产率和选择性氧化为酮，并且催化体系耐受宽范围的O-2浓度而不失活。与其它的铼催化好氧氧化反应相比，该催化体系具有较高的转化率。
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-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).