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

Abstract

This article highlights the recent advances, from 2015 to 2023, on the introduction of organo-fluorine derivatives at the N-heteroarene core. Notable features considering the newer technologies based on organofluorine compounds...

Efficient Trifluoromethylation of Halogenated Hydrocarbons Using Novel [(bpy)Cu(O2CCF2SO2F)2] Reagent

“…Trifluoromethylating agents have garnered significant attention in the field of organic chemistry due to their pivotal role in introducing the trifluoromethyl (CF 3 ) group into molecules [1][2][3][4][5][6][7][8]. This functional group is of paramount importance because of its ability to profoundly influence the physicochemical properties of compounds, making them crucial for the development of pharmaceuticals, agrochemicals, and materials science [9][10][11].…”

Cu-Electrocatalysis Enables Vicinal Bis(difluoromethylation) of Alkenes: Unraveling Dichotomous Role of Zn(CF2H)2(DMPU)2 as Both Radical and Anion Source

“…Due to this high promise of the combinational effect, significant contributions in developing synthetic methods to enable access to such substructures have recently been made. − Among these strategies, difluoromethylative difunctionalization of unsaturated C−C bonds has been pursued as a central strategy to access a range of difluoromethylalkanes, mainly owing to the prevalence of the starting materials and the predictability of the mechanistic pathways involved (Figure C) . Noteworthy progress in this area has been achieved through the generation of CF 2 H radical through single-electron transfer (SET) from various radical precursors, which enables facile installation of CF 2 H to the terminal position of unsaturated C−C bonds and the generation of synthetically versatile secondary alkyl radical intermediate I . ,− The most feasible mechanistic pathway from this intermediate involves rapid single-electron transfer (SET), leading to the formation of the corresponding carbocation that can then readily react with nucleophiles (Figure C, path A, radical-polar crossover). ,,− Alternatively, this intermediate could possibly undergo radical homocoupling if stable enough (path B). ,, …”

Direct Synthesis of 2-Hydroxytrifluoroethylacetophenones via Organophotoredox-Mediated Net-Neutral Radical/Polar Crossover

“…The presence of fluorine or fluorinated groups in a bioactive molecule can provide better metabolic stability, lipophilicity, and binding selectivity . Undoubtedly, the trifluoromethyl group is widely prevalent in many agrochemicals and pharmaceuticals, and extensive attention has been devoted toward the design and development of efficient synthetic methods to provide access to CF 3 -containing organic architectures. In recent years, developments in radical, nucleophilic and electrophilic approaches have advanced in the field using CF 3 I, Langlois, Ruppert–Prakash, Togni, Umemoto reagents, and others.…”