首页> 外文期刊>Chemistry: A European journal >Mechanism of Homogeneously and Heterogeneously Catalysed Meerwein-Ponndorf-Verley-Oppenauer Reactions for the Racemisation of Secondary Alcohols
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Mechanism of Homogeneously and Heterogeneously Catalysed Meerwein-Ponndorf-Verley-Oppenauer Reactions for the Racemisation of Secondary Alcohols

机译:均相和非均相催化的Meerwein-Ponndorf-Verley-Oppenauer反应用于仲醇外消旋化的机理

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The mechanism of hydrogen transfer from alcohols to ketones,catalysed by lanthanide(III)isopropoxides or zeolite Beta has been studied.For the lanthanide catalysed reactions,(S)-1-phenyl-(1-~2H_1)ethanol and acetophe-none were used as case studies to determine the reaction pathway for the hydrogen transfer.Upon complete rac-emisation all deuterium was present at the 1-position,indicating that the reac tion exclusively takes place via a carbon-to-carbon hydrogen transfer.Zeolite Beta with different Si/Al ratios was applied in the racemisation of(S)-1-phenylethanol.In this case the race misation does not proceed via an oxidation/reduction pathway but via elimination of the hydroxy group and its re-addition.This mechanism,however,is not characteristic for all racemisation reactions with zeolite Beta.When 4-tert-butyl cyclohexanone is reduced with this catalyst,a classical MPV reaction takes place exclusively.This demonstrates that zeolite Beta has a substrate dependent reaction pathway.
机译:研究了异丙基镧系元素(III)或β沸石催化氢从醇类向酮类转移的机理。对于镧系元素催化的反应,(S)-1-苯基-(1-〜2H_1)乙醇和乙炔-无用作个案研究以确定氢转移的反应途径。完全消解后,所有氘都存在于1位,表明反应仅通过碳-碳氢转移进行。 (S)-1-苯基乙醇的外消旋作用中使用了不同的Si / Al比。在这种情况下,种族错配不是通过氧化/还原途径进行的,而是通过消除羟基及其重新添加而进行的。但是,并不是所有与β沸石的消旋反应都具有特征。当用这种催化剂还原4-叔丁基环己酮时,经典的MPV反应会发生。这表明β沸石具有与底物有关的反应途径。

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