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Novel heterogeneous ruthenium racemization catalyst for dynamic kinetic resolution of chiral aliphatic amines
Green Chemistry ( IF 9.8 ) Pub Date : 2019-11-21 , DOI: 10.1039/c9gc02615k
Koen Adriaensen 1, 2, 3, 4, 5 , Jannick Vercammen 1, 2, 3, 4, 5 , Cédric Van Goethem 1, 2, 3, 4, 5 , Samuel Eyley 5, 6, 7, 8, 9 , Ivo Vankelecom 1, 2, 3, 4, 5 , Wim Thielemans 5, 6, 7, 8, 9 , Dirk De Vos 1, 2, 3, 4, 5
Affiliation  

Only few dynamic kinetic resolution (DKR) systems are known for chiral aliphatic amines due to the difficult racemization of these amines. In this work, each aspect of the DKR of aliphatic amines is investigated. Various ruthenium catalysts were evaluated to increase their applicability in racemization as an alternative to established heterogeneous palladium catalysts. A heterogeneous Ru(III) on zeolite catalyst showed good activity for racemization in aprotic polar media. Next, kinetic resolution was evaluated; excellent yields (50%) and selectivities (>99%) were obtained in apolar solvents when employing isopentyl propionate as resolving agent. After evaluation of both components, the complete dynamic kinetic resolution of an aliphatic amine was established with good selectivity (97%), enantiomeric excess (96%) and a yield exceeding the kinetic resolution limit of 50%.

中文翻译:

用于手性脂肪族胺动力学动力学拆分的新型异质钌外消旋催化剂

由于手性脂肪族胺的外消旋作用困难,因此只有很少的动力学动力学拆分(DKR)系统是已知的。在这项工作中,对脂族胺的DKR的各个方面进行了研究。对各种钌催化剂进行了评估,以提高它们在外消旋中的适用性,以取代已建立的多相钯催化剂。异质Ru(III)在沸石催化剂上显示出在非质子极性介质中良好的外消旋活性。接下来,评估动力学分辨率;结果示于表1。当使用丙酸异戊酯作为拆分剂时,在非极性溶剂中获得优异的收率(50%)和选择性(> 99%)。在评估了两种成分后,建立了脂族胺的完全动态动力学拆分,具有良好的选择性(97%),对映体过量(96%)和超过了50%的动力学拆分极限的收率。
更新日期:2019-11-21
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