当前位置: X-MOL 学术Nat. Catal. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Iridium-catalysed asymmetric hydrogenation of allylic alcohols via dynamic kinetic resolution
Nature Catalysis ( IF 37.8 ) Pub Date : 2018-05-21 , DOI: 10.1038/s41929-018-0070-0
Jianguo Liu , Suppachai Krajangsri , Jianping Yang , Jia-Qi Li , Pher G. Andersson

Dynamic kinetic resolutions (DKRs) allow for the conversion of both enantiomers of starting material into a single enantiomer of product, hence avoiding the 50% yield limit observed in traditional kinetic resolutions. Transition-metal-catalysed variants have become an important and useful method in asymmetric synthesis. Here we report an asymmetric hydrogenation of allylic alcohols using an Ir–N,P-ligand complex via DKR. In contrast to the many DKRs involving carbonyl reduction, this methodology allows for DKR during alkene reduction. Mechanistic studies support the hypothesis that racemization of the substrate is achieved by cleavage and reforming of the oxygen–carbon bond. Under the cooperative dynamic kinetic asymmetric hydrogenation, a broad range of chiral alcohols containing two stereogenic centres were produced with excellent diastereoselectivities (up to 95:5) and enantioselectivities (up to 99%).



中文翻译:

铱催化的动力学动力学拆分烯丙基醇的不对称加氢反应

动态动力学拆分(DKR)允许将起始原料的两种对映异构体都转化为产品的单个对映异构体,因此避免了传统动力学拆分中观察到的50%的收率限制。过渡金属催化的变体已成为不对称合成中重要且有用的方法。在这里,我们报告通过DKR使用Ir–N,P-配体络合物对烯丙醇进行不对称氢化。与许多涉及羰基还原的DKR相比,此方法可在烯烃还原过程中实现DKR。机理研究支持以下假设:底物的消旋作用是通过氧碳键的裂解和重整来实现的。在协同动力学动力学不对称加氢作用下,

更新日期:2018-05-22
down
wechat
bug