Molecules that contain a stereogenic phosphorus atom are crucial to medicine, agrochemistry and catalysis. While methods are available for the selective construction of various chiral organophosphorus compounds, catalytic enantioselective approaches for their synthesis are far less common. Given the vastness of possible substituent combinations around a phosphorus atom, protocols for their preparation should also be divergent, providing facile access not only to one but to many classes of phosphorus compounds. Here we introduce a catalytic and enantioselective strategy for the preparation of an enantioenriched phosphorus(V) centre that can be diversified enantiospecifically to a wide range of biologically relevant phosphorus(V) compounds. The process, which involves an enantioselective nucleophilic substitution catalysed by a superbasic bifunctional iminophosphorane catalyst, can accommodate a wide range of carbon substituents at phosphorus. The resulting stable, yet versatile, synthetic intermediates can be combined with a multitude of medicinally relevant O-, N- and S-based nucleophiles.

含有立体磷原子的分子对医学、农业化学和催化至关重要。虽然有多种方法可用于选择性构建各种手性有机磷化合物，但用于其合成的催化对映选择性方法却很少见。鉴于磷原子周围可能存在大量取代基组合，它们的制备方案也应该是不同的，不仅可以轻松获得一种磷化合物，还可以轻松获得多种磷化合物。在这里，我们介绍了一种催化和对映选择性策略，用于制备对映体富集的磷 (V) 中心，该中心可以对映体专一地多样化为各种生物学相关的磷 (V) 化合物。过程，它涉及由超碱性双功能亚氨基正膦催化剂催化的对映选择性亲核取代，可以在磷上容纳各种碳取代基。由此产生的稳定但通用的合成中间体可以与多种医学相关的 O-、N- 和 S 基亲核试剂结合。