Zhang Pei-Chao, Li Yin-Lin, He Jiafeng, Wu Hai-Hong, Li Zhiming, Zhang Junliang
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, China.
Department of Chemistry, Fudan University, Shanghai, China.
Nat Commun. 2021 Jul 29;12(1):4609. doi: 10.1038/s41467-021-24678-5.
The simultaneous construction of two different chiralities via a simple operation poses considerable challenge. Herein a cationic gold-catalyzed asymmetric hydroarylation of ortho-alkynylaryl ferrocenes derivatives is developed, which enable the simultaneous construction of axial and planar chirality. The here identified TY-Phos derived gold complex is responsible for the high yield, good diastereoselectivity (>20:1 dr), high enantioselectivities (up to 99% ee) and mild conditions. The catalyst system also shows potential application in the synthesis of chiral biaryl compounds. The cause of high enantioselectivity of this hydroarylation is investigated with density functional theory caculation.
通过简单操作同时构建两种不同的手性面临着巨大挑战。在此，开发了一种阳离子金催化的邻炔基芳基二茂铁衍生物的不对称氢芳基化反应，该反应能够同时构建轴手性和面手性。此处鉴定出的由TY-Phos衍生的金络合物促成了高收率、良好的非对映选择性（>20:1 dr）、高对映选择性（高达99% ee）以及温和的反应条件。该催化体系在手性联芳基化合物的合成中也显示出潜在应用。利用密度泛函理论计算研究了这种氢芳基化反应高对映选择性的原因。
