Recent advances in the functionalization of polyfluoro(aza)aromatics via C–C coupling strategies

Abstract

This review highlights the recent advances in the functionalization of polyfluoro(aza)aromatics via both transition metal-catalyzed and metal-free C–C coupling reactions for the period from 2006 to the beginning of 2021.

Cooperative Bimetallic Catalysis via One‐Metal/Two‐Ligands: Mechanistic Insights of Polyfluoroarylation‐Allylation of Diazo Compounds

“…For the synthesis of polyfluoroaryl molecules, direct CÀ H functionalization of polyfluoroarenes is highly advantageous in terms of the atom-and step-economy. [19][20][21][22][23][24][25][26][27][28][29][30] We envisioned that geminal polyfluoroarylation-allylation of diazo esters in one-pot would offer an approach with unprecedented efficiency for the construction of α-polyfluoroaryl quaternary carbon center with synthetically versatile allylic and ester groups (Scheme 1c). However, substantial challenges remain in the proposed transformation, especially with respect to the effective inhibition of possible side reactions, e.g., allylation of polyfluorene, [23,26] polyfluoroarylation of diazo compounds, [24] diallylation, and β-H elimination [31] etc.…”

Palladium‐Catalyzed Direct C−H Olefination of Polyfluoroarenes with Alkenyl Tosylates

“…Direct C−H functionalization of electron‐deficient polyfluoroarene with alkenyl halides is an attractive alternative for the olefination (Figure 2C) [14] . In 2010, Zhang reported a direct alkenylation of polyfluoroarenes with alkenyl iodides [15] .…”

Photoinduced Defluorinative Branch-Selective Olefination of Multifluoro (Hetero)arenes

“…In particular, polyfluorinated aromatics have notable applications in pharmaceuticals, agrochemicals, and functional materials and in the design and development of novel molecular catalysts . Conventionally, polyfluoro (hetero)­arenes are mainly obtained either from the fluorination reactions of nonfluorinated counterparts or from the cross-coupling-type transformations of prefunctionalized fluoro (hetero)­arenes. , However, these two strategies are often hampered by the need for elaborate starting materials, large amounts of precious organometallic reagents, and/or lengthy synthetic steps. Notably, selective manipulation of the C–F bond in readily accessible (hetero)­arene compounds that are already fluorinated has emerged as an attractive and straightforward approach for the synthesis of various functionalized multifluoro (hetero)­aryl products .…”