通过铑催化的不对称氢化反应获得手性七元环胺。
Access to Chiral Seven-Member Cyclic Amines via Rh-Catalyzed Asymmetric Hydrogenation.
机构信息
College of Chemical Engineering, Zhejiang University of Technology , Hangzhou, Zhejiang 310014, P. R. China.
College of Chemistry and Molecular Sciences, Wuhan University , 430072, Wuhan, P. R. China.
出版信息
Org Lett. 2017 Jul 21;19(14):3855-3858. doi: 10.1021/acs.orglett.7b01726. Epub 2017 Jul 3.
A highly efficient asymmetric hydrogenation of azepine/oxazepine-type seven-member cyclic imine hydrochlorides was successfully developed using Rh/bisphosphine-thiourea ligand ZhaoPhos, affording various chiral seven-member cyclic amines with full conversions, high yields, and excellent enantioselectivities (up to 96% yield, >99% ee). Additionally, this asymmetric hydrogenation can proceed well on gram scale with excellent ee value. Moreover, control experimental results displayed that the anion-bonding interaction between the chloride ion of the substrate and thiourea motif of the ZhaoPhos played an important role to obtain excellent enantioselectivity.
使用 Rh/双膦-硫脲配体 ZhaoPhos，成功开发了一种高效的不对称氢化氮杂环庚烷/氮杂环庚烷型七元环亚胺盐酸盐，以获得各种具有完全转化率、高收率和优异对映选择性（高达 96%的产率，>99%ee）的手性七元环胺。此外，该不对称氢化反应可以在克级规模下进行，ee 值仍然很高。此外，对照实验结果表明，底物的氯离子与 ZhaoPhos 的硫脲基之间的阴离子键相互作用对于获得优异的对映选择性起着重要作用。
Zotero 插件