Rh(II)-catalysed N2-selective arylation of benzotriazoles and indazoles using quinoid carbenes via 1,5-H shift.

An efficient Rh(II)-catalyzed highly selective N2-arylation of benzotriazole, indazole, and 1,2,3 triazole is developed using diazonaphthoquinone. The developed protocol is extended with a wide scope. In addition, late-stage arylation of these scaffolds tethered with bioactive molecules is explored. Control experiments and DFT calculations reveal that the reaction proceeds presumably via nucleophilic addition of the N2 (of the 1H tautomer) center to quinoid-carbene followed by a 1,5-H shift.

Weakly coordinating tert-amide assisted Rh(III)-catalyzed C4-cyanation of indoles: application in photophysical studies.

A rhodium(III)-catalyzed indole C4-selective cyanation is described using the bench-stable, user-friendly electrophilic cyanation agent N-cyano-N-phenyl-p-toluenesulfonamide (NCTS) as a coupling partner. A suitably positioned weakly coordinating tert-amide group was utilized for this site selectivity. The developed protocol proceeded with a broad scope. [Cp*Rh(MeCN)3][SbF6]2 was found to be an effective Rh(III) catalyst for this transformation. An initial study was carried out to know the photophysical properties of the C4-cyanated indole frameworks.

Weakly Coordinating tert-Amide-Assisted Ru(II)-Catalyzed Synthesis of Azacoumestans via Migratory Insertion of Quinoid Carbene: Application in the Total Synthesis of Isolamellarins.

A weakly coordinating tert-amide-directed straightforward method was developed for the synthesis of azacoumestans using the corresponding azaheterocycle derivatives and diazonaphthoquinones under cheap Ru(II)-catalyzed conditions. The reaction proceeds via migratory insertion of quinoid carbene and subsequent Brønstead acid-mediated cyclization. The optimized C2-selective method offered a wide scope of important azaheterocycles. Bioactive natural products like isolamellarins A and B were synthesized via the developed protocol. Preliminary mechanistic studies highlighted the probable mechanistic pathway.

Transition metal catalysed direct construction of 2-pyridone scaffolds through C-H bond functionalizations.

Substituted 2-pyridone is one of the most frequent scaffolds among nitrogen-containing bioactive natural products, pharmaceuticals and organic materials. Besides the classical syntheses to construct this class of molecules, retrosynthetically more straightforward approaches based on transition metal catalysed C-H bond functionalizations have been explored recently. In this review, we have summarized the recent progress in the direct transition metal catalysed construction of substituted 2-pyridone scaffolds via site-selective C-H bond functionalizations.

RhIII -Catalyzed Straightforward Synthesis of Benzophenanthroline and Benzophenanthrolinone Derivatives using Anthranils.

An efficient pot-economic and step-economic RhIII -catalyzed site-selective direct amination/annulation strategy was developed for the synthesis of benzophenanthroline derivatives using quinoline N-oxides and anthranils. The method was further extended to the synthesis of nitrogen-containing extended π-conjugated benzophenanthrolinone derivatives. Late-stage functionalizations of cinchonidine and cinchophen derivatives and synthesis of a bioactive quinolino-indole were achieved.

Direct Pd(II)-Catalyzed Site-Selective C5-Arylation of 2-Pyridone Using Aryl Iodides.

A straightforward Pd(II)-catalyzed general strategy was developed for the C5-selective arylation of the 2-pyridone core with easily available aryl iodides. The transformation was highly regioselective and accomplished with a wide scope and functional group tolerance. Silver nitrate played a crucial role in this direct site-selective arylation. The method was extended to synthesize biologically active molecules.