A trisubstituted chiral Cp^x ligand family is introduced. Based on the disubstituted atropchiral Cp^x ligand scaffold, the introduction of a bulky third substituent at the central position of the Cp ring leads to substantially increased selectivities for rhodium(III)-catalyzed kinetic resolutions and allowed for s-factors of up to 50. Their superiority is demonstrated by kinetic resolutions of phosphinic amides providing access to compounds with stereogenic phosphorus(V) atoms. The unreacted acyclic phosphinic amide and the cyclized product are both obtained in good yields and enantioselectivities. The ligand synthesis capitalizes on a late stage modification and expands the accessible ligand Cp^x ligand portfolio.

中文翻译：

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量身定制的三取代手性Cp ^x Rh ^III催化剂，用于动力学拆分次膦酰胺†

引入了三取代的手性Cp ^x配体家族。基于双取代的惰性手性Cp ^x配体支架，在Cp环的中心位置引入庞大的第三取代基会导致铑（III）催化的动力学拆分的选择性大大提高，并允许s因子高达50。次膦酰胺的动力学拆分证明了它们的优越性，次膦酸酯提供了获取具有立体性磷（V）原子的化合物的途径。未反应的无环次膦酰胺和环化产物均以良好的收率和对映选择性获得。配体合成利用了后期修饰并扩展了可及的配体Cp ^x 配体组合。