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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]

Visible‐light mediated hydrophosphorylation and hydrophosphorylative cyclization reactions using heterogeneous graphitic carbon nitride as the photocatalyst were described. The phosphorus atom radical was generated and allows the radical addition and addition/cyclization sequence, efficiently resulting in the final phosphorylated alkenes and cycles formation. Recyclable, nontoxic and low‐cost heterogeneous graphitic carbon nitride as visible light photocatalyst provides a new opportunity for the hydrophosphorylation and hydrophosphorylative cyclization reactions under the present redox‐neutral conditions. [ABSTRACT FROM AUTHOR]

A three‐component acylation/peroxidation of alkenes through visible‐light photocatalysis was described. The acyl radical was generated by a hydrogen atom transfer process and enabled the radical addition and peroxidation. Various indole‐3‐carbaldehyde and styrene derivatives were subjected to the current visible light photochemical conditions, delivering β‐peroxy‐ketones in moderate to good isolated yields. [ABSTRACT FROM AUTHOR]

We herein described a visible light induced nickel(II)-catalyzed cross-coupling of secondary phosphine oxides with aryl halides. The Ni(I) species and chlorine atom radical Cl˙ were generated via the ligand to metal charge transfer (LMCT) process of the NiCl2(PPh3)2, which allows nickel(IV)-phosphorus species in situ formation, giving various tertiary phosphine oxides under photocatalyst-free conditions. [ABSTRACT FROM AUTHOR]