Diazo quinone or quinone diazide, a class of compound has been recently extensively utilised to introduce naphthol moities into the hydrocarbons or nitrogen-containing heterocycles under transition metal catalysis. The reactions...
An efficient Rh(iii)-catalyzed straightforward strategy was developed for the site-selective tandem C4 arylamination/annulation of indole derivatives with anthranil to provide indoloquinoline moieties.
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 Ncontaining heterocycles and their functionalizations. Arguably, one of the most prominent direct strategy is regioselective CÀ 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 CÀ 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 CÀ H bond functionalizations based on migratory insertion of metal-carbenes and nitrenes.
An efficient Ir(III)-catalyzed straightforward intermolecular N-arylation of acyclic aliphatic amides has been achieved using quinone diazide as a coupling partner. The reaction has been developed under simple and mild reaction conditions with a broad substrate scope. The bidentate picolinamide group is essential for successful transformation. Mechanistic studies and DFT calculations highlighted the migratory insertion-based pathway. The developed method exhibits different reactivities compared to the reactions of acyclic aliphatic amides using related diazo/azide congeners under Rh(III)/Ir(III) catalysis.
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.A mong various known 2-pyridone-based moieties, the Naryl 2-pyridone scaffold is considered as an important structural scaffold due to its frequent presence in pharmaceuticals, drug molecules, and organic materials (Figure 1). 1
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 Nnaphthyl 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 2pyridone derivatives were studied to explore encouraging photophysical properties.
Site-selective insertion of metal-carbenes via C(sp2)−H bond functionalizations is an interesting topic to the synthetic chemistry community. Formations and applications of copper carbene intermediates in recent years become significantly increased due to their cost-effectiveness and versatile reactivities. Further, transformations based on C(sp2)−H insertion using diazo and related compounds and its asymmetric versions under copper catalysed conditions have emerged as a new tool for C−C bond formations. This short review summarizes the selective recent advancements in this field.
Transition metal‐catalyzed direct introduction of phenol/naphthol moieties into the arene/heteroarene CH bonds has been studied using quinone diazides. Generally, the reactions proceed via CH insertions of metal carbenes or migratory insertion of metal carbenes. These arylation reactions are further discussed and extended with selected scope, limitations, and plausible mechanism. Interesting enantioselective reactions to provide stereogenic centers and axial chirality are also described. In this article, the summarized progress in the field of site‐selective arylations into CH bonds of arenes/heteroarenes using quinone diazide class of compounds under transition metal catalysis has been described.
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