Pd(II)-Catalyzed Oxidative Naphthylation of 2-Pyridone through N-H/C-H Activation Using Diarylacetylene as an Uncommon Arylating Agent.

A Pd(II)-catalyzed straightforward oxidative naphthylation of unmasked 2-pyridone derivatives is described using a twofold internal alkyne as a coupling partner. The reaction proceeds through N-H/C-H activation to provide polyarylated N-naphthyl 2-pyridones. An unusual oxidative annulation at the arene C-H bond of the diarylalkyne leads to the formation of polyarylated N-naphthyl 2-pyridones, where the 2-pyridone-attached phenyl ring of the naphthyl ring is polyaryl-substituted. Mechanistic studies and DFT calculations suggest a plausible mechanism based on N-H/C-H activation. The N-naphthyl 2-pyridone derivatives were studied to explore encouraging photophysical properties.

Rh(III)-Catalyzed Weakly Coordinating 2-Pyridone-Directed Oxidative Annulation Using Internal Alkynes: A Reversal in Selectivity.

A rhodium(III)-catalyzed Satoh-Miura type oxidative annulation of N-aryl 2-pyridone derivatives is described using internal alkyne as a coupling partner. A weakly coordinating carbonyl group of the 2-pyridone ring is utilized for this transformation. The reaction proceeds with a broad scope and wide functional group tolerance. The solvent plays an important role in the developed method to furnish a different class of annulated product. A preliminary investigation was carried out to explore the photophysical properties of the obtained polyarylated N-naphthyl 2-pyridones.

Rh(III)-Catalyzed mild straightforward synthesis of quinoline-braced cyclophane macrocycles via migratory insertion.

An efficient Rh(III)-catalyzed straightforward strategy is developed for the synthesis of quinoline braced cyclophane macrocycles via methyl (sp3) C-H functionalization. The method is mild, simple and regioselective with various ring sizes and has good functional group tolerance. The method proceeds via C8-methyl metalation, metal-carbene formation and a subsequent migratory insertion. High dilution is not necessary for this macrocyclization and the only byproduct is nitrogen. A preliminary investigation shows that the C-H metalation step is the rate-determining step.

Straightforward Construction and Functionalizations of Nitrogen-Containing Heterocycles Through Migratory Insertion of Metal-Carbenes/Nitrenes.

Nitrogen-containing heterocycles are widely found in various biologically active substrates, pharmaceuticals, natural products and organic materials. Consequently, the continuous effort has been devoted towards the development of straightforward, economical, environmentally acceptable, efficient and ingenious methods for the synthesis of various N-containing heterocycles and their functionalizations. Arguably, one of the most prominent direct strategy is regioselective C-H bond functionalizations which provide the step and atom economical approaches in the presence of suitable coupling partners. In this context, site-selective migratory insertion of metal carbenes/nitrenes to the desired C-H bonds has proven as a useful tool to access various functionalized nitrogen heterocycles. In this personal account, we highlight some of our contemporary development toward constructing N-containing heterocycles and their direct functionalizations via transition metal catalysed C-H bond functionalizations based on migratory insertion of metal-carbenes and nitrenes.

Rh(iii)-Catalyzed tandem indole C4-arylamination/annulation with anthranils: access to indoloquinolines and their application in photophysical studies.

An efficient Rh(iii)-catalyzed straightforward strategy was developed for the tandem C4 arylamination/annulation of indole derivatives with anthranil to provide indoloquinoline moieties. This method is simple and regioselective with a wide scope and functional group tolerance. Mechanistic studies revealed the important role of the newly installed azacycle in the conversion of O-protected aldoximes to their cyano derivatives. Studies were carried out to explore the promising photophysical properties of the obtained indoloquinoline derivatives.