Recent advances in photocatalytic polyfluoroarylation

Abstract

Polyfluoroaryl compounds belong to privileged moieties and engender distinct properties in many pharmaceuticals, agrochemicals, and materials. Over the past decade, considerable seminal reports and reviews merely pay closed attention to...

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

“…The involvement of multifluoro (hetero)­aryl radical anion II is supported by the detection of the corresponding radical adduct when 1,3,5-trimethoxybenzene was added as the radical scavenger (Scheme d). More importantly, the selective formations of 3a from 4-chloro-tetrafluoropyridine 7a and 7c from 3-chloro-tetrafluoropyridine 7b are in line with the featured reactivities of multifluoro (hetero)­aryl radicals under photoredox conditions (Scheme d) . The generation of the arylsulfonylation intermediate III-a was observed in the absence of a base (Scheme e).…”

“…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 . In this context, visible-light photocatalysis has received a significant amount of attention for C–F bond activation under mild and sustainable conditions . Among the notable precedents, photocatalytic hydrodefluorination, alkylation, arylation, alkenylation, and borylation have been reported to take advantage of multifluorinated (hetero)­arenes as radical precursors or radical acceptors (Scheme a, left).…”

Radical reactions enabled by polyfluoroaryl fragments: photocatalysis and beyond

“…[1][2][3] While processes relying on specific fluorine effects associated with fluoroalkyl moieties have been extensively reviewed, the ability of fluorinated aromatic groups to serve as reactivity-enabling functionality has long been neglected, and existing reviews focus on the functionalization of the polyfluoroarene core. [4][5][6][7][8][9][10][11][12][13][14][15][16] At the same time, polyfluoroarenes are widely used for different purposes of catalysis, [17][18][19][20][21] analytical chemistry, 22,23 biochemistry, [24][25][26][27] and materials science [28][29][30][31] and their applications are well beyond the C-F bond activation. This review aims to highlight the known applications of polyfluoroarenes in organic chemistry of free radicals.…”

Quantifying flattening distortion on the thermodynamics and kinetics of electron transfers of Cu(i) photoredox catalysts

“…Visible-light photoredox catalysis has revolutionized organic synthesis by enabling the activation of small molecules, transforming photonic energy into chemical energy. 1,2 In the last decade, it has been used in the synthesis of various industrially and medicinally relevant compounds, [3][4][5][6][7][8] as well as promoting different types of reactions such as C-C and C-heteroatom bond formation, [9][10][11][12][13][14] dehydrogenation, 15 C-H functionalization, 16,17 polyfluoroarylation, 18 atom transfer radical additions, 14,19 H 2 evolution, 20,21 and CO 2 reduction. 22 Ru(II) polypyridyl complexes (e.g., [Ru(bpy) 3 ] 2+ , (bpy = 2,2′bipyridine)) and Ir(III) phenylpyridine ( ppy) complexes (e.g., Ir ( ppy) 3 ) still dominate the field given their notable photophysical and photochemical properties.…”

“…Visible-light photoredox catalysis has revolutionized organic synthesis by enabling the activation of small molecules, transforming photonic energy into chemical energy. 1,2 In the last decade, it has been used in the synthesis of various industrially and medicinally relevant compounds, 3–8 as well as promoting different types of reactions such as C–C and C–heteroatom bond formation, 9–14 dehydrogenation, 15 C–H functionalization, 16,17 polyfluoroarylation, 18 atom transfer radical additions, 14,19 H 2 evolution, 20,21 and CO 2 reduction. 22…”