Luo Jun, Zhang Tao, Wang Lei, Liao Gang, Yao Qi-Jun, Wu Yong-Jie, Zhan Bei-Bei, Lan Yu, Lin Xu-Feng, Shi Bing-Feng
Department of Chemistry, Zhejiang University, Hangzhou, 310027, China.
School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing, 400030, China.
Angew Chem Int Ed Engl. 2019 May 13;58(20):6708-6712. doi: 10.1002/anie.201902126. Epub 2019 Apr 12.
The discovery of proper ligands to simultaneously modulate the reactivity and effectively control the stereoselectivity is a central topic in the field of enantioselective C-H activation. Herein, we reported the synthesis of axially chiral biaryls by Pd-catalyzed atroposelective C-H olefination. A novel chiral spiro phosphoric acid, STRIP, was identified as a superior ligand for this transformation. A broad range of axially chiral quinoline derivatives were synthesized in good yields with excellent enantioselectivities (up to 98 % ee). Density functional theory was used to gain a theoretical understanding of the enantioselectivities in this reaction.
发现合适的配体以同时调节反应活性并有效控制立体选择性是对映选择性C-H活化领域的核心课题。在此，我们报道了通过钯催化的阻转选择性C-H烯基化反应合成轴手性联芳基化合物。一种新型手性螺环磷酸STRIP被确定为该转化反应的优良配体。一系列轴手性喹啉衍生物以良好的收率和优异的对映选择性（高达98% ee）被合成出来。利用密度泛函理论对该反应中的对映选择性进行了理论理解。
