Recent advances on non-precious metal-catalysed fluorination, difluoromethylation, trifluoromethylation, and perfluoroalkylation of N-heteroarenes.

This review highlights the recent advances, from 2015 to 2023, on the introduction of organo-fluorine derivatives at the N-heteroarene core. Notable features considering new technologies based on organofluorine compounds such as: (i) approaches based on non-precious metal catalysis (Fe, Co, Mn, Ni, etc.), (ii) the development of new strategies using non-precious metal-catalysts for the introduction of organo-fluorinine derivatives using N-heterocycles with one or more heteroatoms, (iii) newer reagents for fluorination, difluoromethylation, trifluoromethylation, or perfluoroalkylation of N-heteroarenes using different approaches, (iv) mechanistic studies on various catalytic transformations, as and when required, and (v) the synthetic applications of various bio-active organo-fluorine compounds, including post-synthetic drug derivatization, are discussed.

Nickel-Catalyzed Alkylation of Oxindoles with Secondary Alcohols.

Herein, we have demonstrated a simple nickel-catalyzed C-3-selective alkylation of 2-oxindoles using a wide variety of secondary alkyl alcohols. As a special highlight, functionalization of the cholesterol derivative was reported. Control experiments, initial mechanistic studies, and deuterium-labeling experiments were performed for the alkylation process.

Recent advances on non-precious metal-catalyzed C-H functionalization of N-heteroarenes.

N-Heteroarenes are widely used for numerous medicinal applications, lifesaving drugs and show utmost importance as intermediates in chemical synthesis. This feature article highlights the recent advances, from 2015 to August 2021, on sp2 and sp3 C-H bond functionalization reactions of various N-heteroarenes catalyzed by non-precious transition metals (Mn, Co, Fe, Ni, etc.). The salient features of the report are: (i) the development of newer catalysis for Csp2-H activation of N-heteroarenes and categorized into alkylation, alkenylation, borylation, cyanation, and annulation reactions, (ii) recent advances on Csp3-H bond functionalization of N-heteroarenes considering newer approaches for alkylation as well as alkenylation processes, and (iii) synthetic applications and practical utility of the catalytic protocols utilized for late-stage drug development; (iv) scope for the development of newer catalytic protocols along with mechanistic studies and detail mechanistic findings of various important processes.

Recent advances in the synthesis of N-heteroarenes via catalytic dehydrogenation of N-heterocycles.

Bio-active molecules having N-heteroarene core are widely used for numerous medicinal applications and as lifesaving drugs. In this direction, dehydrogenation of partially saturated aromatic N-heterocycles shows utmost importance for the synthesis of heterocycles. This feature article highlights the recent advances, from 2009 to April 2021, on the dehydrogenation of N-heteroaromatics. Notable features considering the development of newer catalysis for dehydrogenations are: (i) approaches based on precious metal catalysis, (ii) newer strategies and catalyst development technology using non-precious metal-catalysts for N-heterocycles having one or more heteroatoms, (iii) Synthesis of five or six-membered N-heterocycles using photocatalysis, electrocatalytic, and organo-catalytic approaches using different homogeneous and heterogeneous conditions' (iv) metal free (base and acid-promoted) dehydrogenation along with I2, N-hydroxyphthalimide (NHPI) and bio catalyzed miscellaneous examples have also been discussed, (v) mechanistic studies for various dehydrogenation reactions and (vi) synthetic applications of various bio-active molecules including post-drug derivatization are discussed.

Nickel-Catalyzed Dehydrogenation of N-Heterocycles Using Molecular Oxygen.

Herein, an efficient and selective nickel-catalyzed dehydrogenation of five- and six-membered N-heterocycles is presented. The transformation occurs in the presence of alkyl, alkoxy, chloro, free hydroxyl and primary amine, internal and terminal olefin, trifluoromethyl, and ester functional groups. Synthesis of an important ligand and the antimalarial drug quinine is demonstrated. Mechanistic studies revealed that the cyclic imine serves as the key intermediate for this stepwise transformation.

Nickel-catalyzed hydrogen-borrowing strategy: chemo-selective alkylation of nitriles with alcohols.

The first nickel-catalyzed hydrogen-borrowing alkylation of a series of aryl acetonitriles with a variety of aryl, heteroaryl, allylic and alkyl alcohols releasing water as the by-product (>33 examples, up to 90% yield) is reported.

Nickel-catalysed dehydrogenative coupling of aromatic diamines with alcohols: selective synthesis of substituted benzimidazoles and quinoxalines.

The first nickel-catalysed dehydrogenative coupling of primary alcohols and ethylene glycol with aromatic diamines for selective synthesis of mono- and di-substituted benzimidazoles and quinoxalines is reported. The earth-abundant, non-precious and simple NiCl2/L1 system enables the synthesis of N-heterocycles releasing water and hydrogen gas as byproducts. Mechanistic studies involving deuterium labeling experiments and quantitative determination of hydrogen gas evaluation were performed.