How Rhodium(I)-Catalyzed Phosphorus(III)-Directed C–H Bond Functionalizations Can Improve the Catalytic Activities of Phosphines

Trivalent-phosphorus-containing molecules are widely used in fields ranging from catalysis to materials science. Efficient catalytic methods for their modifications, providing straightforward access to novel hybrid structures with superior catalytic activities, are highly desired to facilitate reaction improvement or discovery. We have recently developed new methods for synthesizing polyfunctional phosphines by C–C cross-couplings through rhodium-catalyzed C–H bond activation. These methods use a native P(III) atom as a directing group, and can be used in regioselective late-stage functionalization of phosphine ligands. Interestingly, some of the modified phosphines outperform their parents in Pd-catalyzed cross-coupling reactions.1 Introduction2 Early Examples of Transition-Metal-Catalyzed P(III)-Directed C–H Bond Activation/Functionalizations3 Synthesis of Polyfunctional Biarylphosphines by Late-Stage Alkylation: Application in Carboxylation Reactions4 Synthesis of Polyfunctional Biarylphosphines by Late-Stage Alkenylation: Application in Amidation Reactions5 Conclusion

RhIII-catalyzed heteroarylation of N-2,6-difluorophenyl arylamides with heteroaryl boronate esters

Herein, an efficient strategy to aryl-heteroaryl formation via RhIII-catalyzed ortho-C(sp2)−H heteroarylation of (hetero)arenes with heterocyclic boronates using a readily removable N-2,6-difluorophenyl arylamides directing group has been disclosed. A variety of...

Pd and photoredox dual catalysis assisted decarboxylative ortho-benzoylation of N-phenyl-7-azaindoles

Directing group assisted decarboxylative ortho-benzoylation of N-aryl-7-azaindoles with α-keto acids has been achieved by synergistic visible light promoted photoredox and palladium catalysis. The approach tenders rapid entry to aryl ketone...

Cobalt-Catalyzed Highly Diastereoselective [3+2] Carboannulation Reaction: Facile Access to Substituted Indane Derivatives

An efficient oxidative [3+2] annulation reaction of aryl hydrazones and heterobicyclic alkenes has been realized with inexpensive and earth-abundant cobalt-salts under aerobic conditions. The reaction proceeds via directing-group assisted C-H...

Tandem cyclization/arylation of diaryliodoniums via in situ constructed benzoxazole as a directing group for atom-economical transformation

Linear diaryliodoniums often undergo only single arylation and leave equivalent aryliodide as waste. Herein, we demonstrate that linear unsymmetrical diaryliodoniums could be tuned by dual nickel/palladium metal system to accomplish...