Modular Synthesis of Polysubstituted α-Phosphorylated Arenes via the Catellani Strategy

In this paper, we described a palladium/norbornene-catalyzed ortho-C–H phosphormethylation of aryl iodides using XCH2P(O)RR′, offering a reliable method for the modular synthesis of polysubstituted α-phosphorylated arenes. Alkenylation, hydrogenation, cyanation, methylation, and arylation were all viable termination steps compatible with the reaction. This method demonstrates excellent functional group tolerance and can be extended to the late-stage modification of bioactive molecules. Furthermore, the synthetic transformations of the products demonstrate the practical utility of this reaction.