Late‐Stage Diversification of Carbazolyl‐Derived Phosphines via Ru(II)‐Catalyzed P(III)‐Directed C─H Alkenylation With Internal Alkynes

We report a ruthenium‐catalyzed P(III)‐directed ortho ‐C─H alkenylation of carbazolyl‐derived phosphines with internal alkynes. The trivalent phosphorus atom serves as an efficient directing group, enabling the highly selective synthesis of monoalkenylated phosphines in moderate to good yields. By tuning the reaction conditions, the corresponding dialkenylated products can also be obtained in acceptable yields. This protocol provides a straightforward and versatile route to a diverse library of functionalized PhenCarPhos‐type ligands. Notably, these ligands exhibit superior catalytic performance to common commercially available or unfunctionalized phosphines in the palladium‐catalyzed amination of aryl chlorides with morpholine.