Wu Le-Song, Wang Chen-Yue, Zhou Tao, Shi Bing-Feng
Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou 310027, China.
College of Material Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, Hangzhou 311121, Zhejiang, China.
Org Lett. 2024 Oct 25;26(42):8988-8992. doi: 10.1021/acs.orglett.4c02692. Epub 2024 Oct 14.
Chiral phosphorus compounds with contiguous ,-stereogenic centers are widely found in chiral ligands. The synthesis of these skeletons has been scarcely reported. Herein, we developed a Pd(II)-catalyzed chemo-, diastereo-, and enantioselective arylation of diisopropyl phosphinamide enabled by 2-pyridinylisopropyl (PIP) auxiliary and ()-6,6'-(CN)-SPINOL. A range of chiral phosphinamides containing contiguous ,-stereocenters were obtained in good yields (up to 85%) with excellent enantioselectivities (up to >99% ee).
在手性配体中广泛存在具有相邻α,β-手性中心的手性磷化合物。关于这些骨架的合成报道极少。在此，我们开发了一种由2-吡啶基异丙基（PIP）辅助剂和（）-6,6'-（氰基）-SPINOL实现的钯（II）催化的二异丙基膦酰胺的化学、非对映和对映选择性芳基化反应。一系列含有相邻α,β-手性中心的手性膦酰胺以良好的产率（高达85%）和优异的对映选择性（高达>99% ee）得到。
