Sun Jinghui, Yan Yifei, Chen Xuanxuan, Huang Zhiwei, Huang Yinhua
College of Materials, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University Hangzhou 311121 P. R. China
Chem Sci. 2024 Apr 9;15(18):6943-6948. doi: 10.1039/d4sc00446a. eCollection 2024 May 8.
A palladium-catalyzed regio- and stereo-selective phosphination of cyclic biarylsulfonium salts (racemic) with HPArAr for straightforward synthesis of atropoisomeric phosphines (P,S-ligands) bearing a stereogenic axis or both a stereogenic axis and a P-stereogenic center is reported. The high reactivity and regio- and stereo-selectivity originate from the torsional strain release and palladium catalysis, and the construction of a P-stereogenic center is enabled by an efficient dynamic kinetic resolution. The high performance of the nascent P,S-ligands has been demonstrated in palladium-catalyzed asymmetric allylic substitutions, indicating the great potential of the present methodology.
报道了一种钯催化的环状联芳基硫鎓盐（外消旋体）与HPArAr的区域和立体选择性膦化反应，用于直接合成具有手性轴或同时具有手性轴和P-手性中心的阻转异构膦（P，S-配体）。高反应活性以及区域和立体选择性源于扭转应变释放和钯催化，并且通过有效的动态动力学拆分实现了P-手性中心的构建。新生的P，S-配体在钯催化的不对称烯丙基取代反应中表现出高性能，表明本方法具有巨大潜力。
