Organophosphines are an important class of ligands widely used in organic chemistry. Although great progress has recently been made in the rapid construction of new phosphines through Rh- or Ru-catalyzed C–H bond functionalizations, synthetic access to more diverse phosphines remains a challenge. We describe an efficient process for the rhodium-catalyzed phosphorus(III)-directed hydroarylation of internal alkynes to generate various alkenylated and 2′,6′-dialkenylated biarylphosphines with high selectivity. A range of diverse alkynes and phosphines were effectively prepared with broad functional-group compatibility under the optimized conditions. In addition, the developed protocol can be extended to modify chiral phosphine ligands, providing enantioenriched alkenylated phosphines without erosion of the enantiomeric excess.

中文翻译：

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铑催化的内部炔烃进行磷（III）定向的氢芳基化反应：轻松有效地获得新的膦配体

有机膦是广泛用于有机化学中的重要一类配体。尽管最近通过Rh或Ru催化的C–H键功能化在快速构建新的膦化合物方面取得了巨大进展，但合成合成更多种类的膦仍然是一个挑战。我们描述了一种高效的铑催化内部炔烃的磷（III）定向加氢芳基化反应，以产生具有高选择性的各种烯基化和2'，6'-二烯基化联芳基膦。在优化的条件下，可以有效制备具有广泛的官能团相容性的各种炔烃和膦。另外，可以扩展已开发的方案以修饰手性膦配体，提供对映体富集的烯基化膦，而不会侵蚀对映体过量。