Li Xiuxiu, You Cai, Yang Yusheng, Yang Yuhong, Li Pan, Gu Guoxian, Chung Lung Wa, Lv Hui, Zhang Xumu
Key Laboratory of Biomedical Polymers of Ministry of Education , College of Chemistry and Molecular Sciences , Wuhan University , Wuhan , Hubei 430072 , P. R. China . Email:
Department of Chemistry , Southern University of Science and Technology , Shenzhen , Guangdong 518055 , P. R. China . Email:
Chem Sci. 2018 Jan 4;9(7):1919-1924. doi: 10.1039/c7sc04639a. eCollection 2018 Feb 21.
With the assistance of hydrogen bonds, the first asymmetric hydrogenation of β-cyanocinnamic esters is developed, affording chiral β-cyano esters with excellent enantioselectivities (up to 99% ee). This novel methodology provides an efficient and concise synthetic route to chiral GABA-derivatives such as ()-Pregabalin, ()-Phenibut, ()-Baclofen. Interestingly, in this system, the catalyst with a single H-bond donor performs better than that with double H-bond donors, which is a novel discovery in the metalorganocatalysis area.
在氢键的辅助下，实现了β-氰基肉桂酸酯的首例不对称氢化反应，得到了对映选择性优异（高达99% ee）的手性β-氰基酯。这种新颖的方法为合成手性γ-氨基丁酸衍生物，如（）-普瑞巴林、（）-苯丁胺、（）-巴氯芬，提供了一条高效且简洁的合成路线。有趣的是，在该体系中，具有单个氢键供体的催化剂比具有双氢键供体的催化剂表现更好，这是金属有机催化领域的一个新发现。
