MTO与OsO4：用于基于过氧化氢的烯烃温和不对称二羟基化反应的高效催化组合。
MTO and OsO4: an efficient catalytic couple for mild H2O2-based asymmetric dihydroxylation of olefins.
作者信息
Jonsson Sandra Y, Adolfsson Hans, Bäckvall Jan-E
机构信息
Department of Organic Chemistry, Stockholm University, Sweden.
出版信息
Chemistry. 2003 Jun 16;9(12):2783-8. doi: 10.1002/chem.200304828.
A novel and robust system for osmium-catalyzed asymmetric dihydroxylation of olefins by aqueous H2O2 with methyltrioxorhenium (MTO) as electron transfer mediator (ETM) has been developed. The MTO is catalyzing the H2O2 oxidation of the chiral ligand to its mono-N-oxide, which in turn reoxidizes OsVI to OsVIII. Thus the (DHQD)2PHAL plays a dual role serving as the chiral inductor as well as the tertiary amine generating the N-oxide required for the recycling of osmium. The present catalytic system gives vicinal diols in good isolated yields and high enantiomeric excess (up to 99 % ee).
已开发出一种新颖且稳健的体系，用于在水相过氧化氢存在下，以甲基三氧化铼（MTO）作为电子转移介质（ETM），实现锇催化的烯烃不对称二羟基化反应。MTO催化手性配体被过氧化氢氧化为其一N - 氧化物，该N - 氧化物进而将OsVI再氧化为OsVIII。因此，(DHQD)2PHAL起到双重作用，既作为手性诱导剂，又作为叔胺生成锇循环所需的N - 氧化物。目前的催化体系能以良好的分离产率和高对映体过量（高达99% ee）得到邻二醇。
Zotero 插件