Department of Chemistry, National University of Singapore, 3 Science Drive 3, Republic of Singapore, 117543.
J Am Chem Soc. 2015 Apr 22;137(15):4944-7. doi: 10.1021/jacs.5b02212. Epub 2015 Apr 8.
The first dynamic kinetic asymmetric amination of alcohols via borrowing hydrogen methodology is presented. Under the cooperative catalysis by an iridium complex and a chiral phosphoric acid, α-branched alcohols that exist as a mixture of four isomers undergo racemization by two orthogonal mechanisms and are converted to diastereo- and enantiopure amines bearing adjacent stereocenters. The preparation of diastereo- and enantiopure 1,2-amino alcohols is also realized using this catalytic system.
本文首次提出了通过借氢方法实现的醇的动态动力学非对映选择性胺化反应。在手性磷酸和铱配合物的协同催化作用下，α-支链醇（四种异构体的混合物）通过两种正交机制发生外消旋化，并转化为具有相邻手性中心的非对映和对映纯胺。该催化体系还可用于制备非对映和对映纯 1,2-氨基醇。
