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Fast Racemisation of Chiral Amines and Alcohols by Using Cationic Half-Sandwich Ruthena- and Iridacycle Catalysts

机译:使用阳离子半三明治钌和铱化合物催化快速消旋手性胺和醇

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摘要

The lipase-catalysed resolution of alcohols and amines yields only 50% of the desired enantiopure product. However, addition of a racemisation catalyst leads to 100% yield in what is called a dynamic kinetic resolution (DKR). There is a need for new racemisation catalysts that are fast and compatible with the conditions of the enzymatic reaction. We show that cationic half-sandwich ruthena- and iridacycle complexes are highly active and efficient in the racemisation of chiral alcohols and amines. Upon activation with base, these complexes are able to selectively racemise alcohols, whereas the non-activated complexes are selective catalysts for the racemisation of amines. We have applied the iridacycles in the DKR of racemic beta-chloroalcohols to produce chiral epoxides in a biphasic system in good yields and high ee (ee = enantiomeric excess).
机译:脂肪酶催化的醇和胺的拆分仅产生所需对映体纯产物的50%。然而,外消旋催化剂的添加导致100%的所谓动态动力学拆分(DKR)产率。需要快速且与酶促反应条件相容的新型外消旋化催化剂。我们表明,阳离子半三明治钌-和iridacycle配合物在手性醇和胺的外消旋中具有很高的活性和效率。在用碱活化后,这些络合物能够选择性消旋醇,而未活化的络合物是胺消旋的选择性催化剂。我们已将消旋环应用于外消旋β-氯醇的DKR中,从而在双相体系中以高收率和高ee(ee =对映体过量)生产手性环氧化物。

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