Feng Guang-Shou, Chen Mu-Wang, Shi Lei, Zhou Yong-Gui
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
University of Chinese Academy of Sciences, Beijing, 100049, China.
Angew Chem Int Ed Engl. 2018 May 14;57(20):5853-5857. doi: 10.1002/anie.201801485. Epub 2018 Apr 17.
A facile access to optically active cyclic ureas was developed through palladium-catalyzed asymmetric hydrogenation of pyrimidines containing tautomeric hydroxy group with up to 99 % ee. Mechanistic studies indicated that reaction pathway proceed through hydrogenation of C=N of the oxo tautomer pyrimidin-2(1H)-one, acid-catalyzed isomerization of enamine-imine, and hydrogenation of imine pathway. In addition, the chiral cyclic ureas are readily converted into useful chiral 1,3-diamine and thiourea derivatives without loss of optical purity.
通过钯催化含有互变异构羟基的嘧啶的不对称氢化反应，开发了一种简便合成光学活性环状脲的方法，对映体过量值（ee）高达99%。机理研究表明，反应途径是通过氧代互变异构体嘧啶-2(1H)-酮的C=N氢化、酸催化的烯胺-亚胺异构化以及亚胺途径的氢化。此外，手性环状脲很容易转化为有用的手性1,3-二胺和硫脲衍生物，且不会损失光学纯度。
