Merging Visible Light Photocatalysis and P(III)‐Directed C−H Activation by a Single Catalyst: Modular Assembly of P‐Alkyne Hybrid Ligands.

Metal‐catalyzed C−H activation strategies provide an efficient approach for synthesis by minimizing atom, step, and redox economy. Developing milder, greener, and more effective protocols for these strategies is always highly desirable to the scientific community. In this study, the utilization of a single rhodium complex enabled the visible‐light‐induced late‐stage C−H activation of biaryl‐type phosphines with alkynyl bromides, employing inherent phosphorus atoms as directing groups. This chemistry combines P(III)‐directed C−H activation with visible light photocatalysis, under exogenous photosensitizer‐free conditions, offering a unique platform for ligand design and preparation. Furthermore, this study also explores the asymmetric catalysis and coordination chemistry of the resulting P‐alkyne hybrid ligands with specific transition metals. Experimental results and density functional theory calculations demonstrate the mechanistic intricacies of this transformation. [ABSTRACT FROM AUTHOR]