journal article·2024-10Open access

Catalyst-free electrochemical SNAr of electron-rich fluoroarenes using carboxylic acids

Anzai Shi, Yaowen Liu, Ranran Zhang, Zile Zhu, Youai Qiu

eScience· Volume 4· Issue 5

Abstract

Herein, an electrochemically driven catalyst-free nucleophilic aromatic substitution (SNAr) of electron-rich fluoroarenes with carboxylic acids as weak nucleophiles under mild conditions was reported. A series of highly valuable ester derivatives were obtained in a direct and rapid way. This transformation features commercially available reagents and an exceptionally broad substrate scope with good functional group tolerance, using cheap and abundant electrodes and completed within a short reaction time. Gram-scale synthesis and complex biorelevant compounds ligation further highlighted the potential utility of the methodology. The mechanistic investigations and density functional theory (DFT) calculations verified the feasibility of the proposed pathway of this transformation.
Source: openalex_inverted_index · Quality: baseline

Research context

OpenAlex topics: Catalytic C–H Functionalization Methods · Sulfur-Based Synthesis Techniques · Radical Photochemical Reactions

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (98)

Show source-provided references
1. Aromatic nucleophilic substitution reactions10.1021/cr60153a002 ↗
2. Nucleophilic replacement of the nitro group, fluorine and chlorine in aromatic compounds10.1070/RC2003v072n08ABEH000809 ↗
3. Nucleophilic substitution reactions by electron transfer10.1021/cr960134o ↗
4. Organocatalytic regio- and asymmetric C-selective SNAr reactions−stereoselective synthesis of optically active spiro-pyrrolidone-3,3‘-oxoindoles10.1021/ja050200g ↗
5. Meisenheimer complexes in SNAr reactions: intermediates or transition states?10.1002/anie.201809606 ↗
6. Concerted nucleophilic aromatic substitution reactions10.1002/anie.201902216 ↗
7. SNAr isocyanide diversification10.1002/ejoc.202101023 ↗
8. Nucleophilic amination of methoxy arenes promoted by a sodium hydride/iodide composite10.1002/anie.201705916 ↗
9. Cation radical accelerated nucleophilic aromatic substitution via organic photoredox catalysis10.1021/jacs.7b10076 ↗
10. 19F- and 18F-arene deoxyfluorination via organic photoredox-catalysed polarity-reversed nucleophilic aromatic substitution10.1038/s41929-020-0495-0 ↗
11. SNAr and C–H amination of electron rich arenes with pyridine as a nucleophile using photoredox catalysis10.1021/acs.orglett.1c01749 ↗
12. 11C-, 12C-, and 13C-cyanation of electron-rich arenes via organic photoredox catalysis10.1016/j.chempr.2022.12.007 ↗
13. Nucleophilic aromatic substitution (SNAr) as an approach to challenging carbohydrate–aryl ethers10.1021/acs.orglett.5b02413 ↗
14. Silyldefluorination of fluoroarenes by concerted nucleophilic aromatic substitution10.1002/anie.201808646 ↗
15. Synthesis of emissive heteroacene derivatives via nucleophilic aromatic substitution10.1021/acs.joc.9b02523 ↗
16. Nucleophilic aromatic substitution of unactivated aryl fluorides with primary aliphatic amines by organic photoredox catalysis10.1002/chem.202002315 ↗
17. Phosphinylation of non-activated aryl fluorides through nucleophilic aromatic substitution at the boundary of concerted and stepwise mechanisms10.1002/anie.202013544 ↗
18. Nucleophilic aromatic substitution of non-activated aryl fluorides with aliphatic amides10.1039/D2CC02999E ↗
19. Catalytic SNAr hydroxylation and alkoxylation of aryl fluorides10.1002/anie.202106440 ↗
20. Nickel-catalyzed amination of aryl fluorides with primary amines10.1039/C7CC08181B ↗
21. Efficient aryl–(hetero)aryl coupling by activation of C–Cl and C–F bonds using nickel complexes of air-stable phosphine oxides10.1002/anie.200501860 ↗
22. Ligand-free iron-catalyzed C–F amination of diarylamines: a one-pot regioselective synthesis of diaryl dihydrophenazines10.1021/acs.orglett.8b03702 ↗
23. Visible light photoredox catalysis with transition metal complexes: applications in organic synthesis10.1021/cr300503r ↗
24. Asymmetric catalysis activated by visible light10.1039/C4CC09268F ↗
25. Introduction: photochemistry in organic synthesis10.1021/acs.chemrev.6b00378 ↗
26. Strategies for the photocatalytic generation of carbanion equivalents for reductant-free C–C Bond formations10.1021/acs.accounts.0c00620 ↗
27. Recent advances in transition-metal-catalysed asymmetric coupling reactions with light intervention10.1039/D1CS00210D ↗
28. High-performance CsPbBr3@Cs4PbBr6/SiO2 nanocrystals via double coating layers for white light emission and visible light communication10.1016/j.esci.2022.10.005 ↗
29. Oxidase-type C−H/C−H coupling using an isoquinoline-derived organic photocatalyst
30. Introduction: photochemical catalytic processes10.1021/acs.chemrev.1c00993 ↗
31. Photoredox-catalyzed C–H functionalization reactions10.1021/acs.chemrev.1c00311 ↗
32. Porous fixed-bed photoreactor for boosting C–C coupling in photocatalytic CO2 reduction10.1016/j.esci.2022.06.006 ↗
33. Visible light-induced transition metal catalysis10.1021/acs.chemrev.1c00403 ↗
34. Cross-coupling of amines via photocatalytic denitrogenation of in situ generated diazenes10.1021/jacs.3c03634 ↗
35. Metallaphotoredox-enabled aminocarboxylation of alkenes with CO210.1038/s41929-023-01029-9 ↗
36. Benzylic C–H esterification with limiting C–H substrate enabled by photochemical redox buffering of the Cu catalyst10.1021/jacs.3c01662 ↗
37. Photoelectrocatalytic arene C–H amination10.1038/s41929-019-0231-9 ↗
38. Synthetic photoelectrochemistry10.1002/anie.201913767 ↗
39. Reductive electrophotocatalysis: merging electricity and light to achieve extreme reduction potentials10.1021/jacs.9b10678 ↗
40. Research progress in organic synthesis by means of photoelectrocatalysis10.1002/tcr.202000186 ↗
41. Electrophotocatalysis: combining light and electricity to catalyze reactions10.1021/jacs.2c01914 ↗
42. Transition-metal-free, site-selective C–F arylation of polyfluoroarenes via electrophotocatalysis10.1021/jacs.2c08068 ↗
43. Photoelectrochemical asymmetric catalysis enables enantioselective heteroarylcyanation of alkenes via C–H functionalization10.1021/jacs.3c07146 ↗
44. Electrophotocatalytic SNAr reactions of unactivated aryl fluorides at ambient temperature and without base10.1002/anie.201909983 ↗
45. Cation radical-accelerated nucleophilic aromatic substitution for amination of alkoxyarenes10.1021/acs.orglett.0c01621 ↗
46. Photoredox and vanadate cocatalyzed hydrolysis of aryl ethers at ambient temperature10.1021/acscatal.3c02301 ↗
47. Nucleophilic aromatic substitution of unactivated fluoroarenes enabled by organic photoredox catalysis10.1021/jacs.0c09296 ↗
48. Radicals as exceptional electron-withdrawing groups: nucleophilic aromatic substitution of halophenols via homolysis-enabled electronic activation10.1021/jacs.2c10296 ↗
49. Synthetic organic electrochemical methods since 2000: on the verge of a renaissance10.1021/acs.chemrev.7b00397 ↗
50. Electrifying organic synthesis10.1002/anie.201711060 ↗
51. Organic electrochemistry and a role reversal: using synthesis to optimize electrochemical methods10.1021/jacs.8b02922 ↗
52. Powering the future: how can electrochemistry make a difference in organic synthesis?10.1016/j.chempr.2020.08.025 ↗
53. Organic electrochemistry: molecular syntheses with potential10.1021/acscentsci.0c01532 ↗
54. Electrochemical oxidative C3 acyloxylation of imidazo[1,2-a]pyridines with hydrogen evolution10.1021/acs.orglett.1c02032 ↗
55. Electrochemical oxidation induced selective C–C bond cleavage10.1021/acs.chemrev.0c00335 ↗
56. Chemoselective, scalable nickel-electrocatalytic O-arylation of alcohols10.1002/anie.202107820 ↗
57. The applications of electrochemical synthesis in asymmetric catalysis
58. Advances on the merger of electrochemistry and transition metal catalysis for organic synthesis10.1021/acs.chemrev.1c00614 ↗
59. Cathodic carbonyl alkylation of aryl ketones or aldehydes with unactivated alkyl halides10.1021/acs.orglett.2c04019 ↗
60. Enantioselective nickel-catalyzed electrochemical radical allylation
61. Recent progress in cathodic reduction-enabled organic electrosynthesis: trends, challenges, and opportunities10.1016/j.esci.2022.04.006 ↗
62. Electrochemical gold-catalysed biocompatible C(sp2)–C(sp) coupling10.1038/s44160-022-00219-w ↗
63. Electrochemical C3 acyloxylation reactions of 2H-indazoles with carboxylic acids via C(sp2)–O coupling10.1039/D3GC02175K ↗
64. Electrocatalytic access to azetidines via intramolecular allylic hydroamination: scrutinizing key oxidation steps through electrochemical kinetic analysis10.1021/jacs.3c03172 ↗
65. Enantioselective reductive cross-couplings of olefins by merging electrochemistry with nickel catalysis10.1021/jacs.3c10109 ↗
66. Electrochemically mediated decarboxylative acylation of N-nitrosoanilines with α-oxocarboxylic acids
67. Electrochemically generated carbanions enable isomerizing allylation and allenylation of aldehydes with alkenes and alkynes10.1021/jacs.3c04864 ↗
68. Electrochemical C−H amination by cobalt catalysis in a renewable solvent10.1002/anie.201802206 ↗
69. Chemical-reductant-free electrochemical deuteration reaction using deuterium oxide10.1002/anie.202005765 ↗
70. Electroreductive cobalt-catalyzed carboxylation: cross-electrophile electrocoupling with atmospheric CO210.1002/anie.202003218 ↗
71. Site-selective electrochemical benzylic C−H amination10.1002/anie.202013478 ↗
72. Electrochemically induced nickel catalysis for oxygenation reactions with water10.1038/s41929-020-00559-w ↗
73. Electrocatalytic radical-polar crossover hydroetherification of alkenes with phenols10.1021/acscatal.2c02436 ↗
74. Electrochemical palladium-catalyzed oxidative carbonylation-cyclization of enallenols10.1002/anie.202212131 ↗
75. Electrochemical PINOylation of methylarenes: improving the scope and utility of benzylic oxidation through mediated electrolysis10.1021/jacs.2c05974 ↗
76. Organoboron reagent-controlled selective (deutero)hydrodefluorination10.1002/anie.202217244 ↗
77. Electrochemical reactor dictates site selectivity in N-heteroarene carboxylations10.1038/s41586-022-05667-0 ↗
78. Electroreductive dicarboxylation of unactivated skipped Dienes with CO2
79. Electrochemically driven deoxygenative borylation of alcohols and carbonyl compounds10.1021/jacs.3c03418 ↗
80. Electrooxidative activation of B−B bond in B2cat2: access to gem-diborylalkanes via paired electrolysis
81. Complex molecule synthesis by electrocatalytic decarboxylative cross-coupling10.1038/s41586-023-06677-2 ↗
82. Enantioselective nickel-catalysed electrochemical cross-dehydrogenative amination10.1038/s44160-023-00372-w ↗
83. Electrophotoredox/cerium-catalyzed unactivated alkanes activation for the sustainable synthesis of alkylated benzimidazo-fused isoquinolinones10.1016/j.jcat.2022.12.033 ↗
84. Selective synthesis of partially protected nonsymmetric biphenols by reagent- and metal-free anodic cross-coupling reaction10.1002/anie.201604321 ↗
85. Electrogenerated cationic reactive intermediates: the pool method and further advances10.1021/acs.chemrev.7b00475 ↗
86. Electrooxidative para-selective C–H/N–H cross-coupling with hydrogen evolution to synthesize triarylamine derivatives10.1038/s41467-019-08414-8 ↗
87. Photoelectrocatalytic C–H amination of arenes10.1039/D3GC02126B ↗
88. Metal-free electrochemical carboxylation of organic halides in the presence of catalytic amounts of an organomediator
89. Metal-free electrochemical dihydroxylation of unactivated alkenes10.1038/s41467-023-42106-8 ↗
90. Electrochemical NiH-catalyzed C(sp3)−C(sp3) coupling of alkyl halides and alkyl alkenes
91. Solvent control in electro-organic synthesis10.1055/s-0037-1610303 ↗
92. C–H bond activation enables the rapid construction and late-stage diversification of functional molecules10.1038/nchem.1607 ↗
93. Late-stage C–H functionalization offers new opportunities in drug discovery10.1038/s41570-021-00300-6 ↗
94. Visible light photocatalysis in the late-stage functionalization of pharmaceutically relevant compounds10.1039/D0CS00493F ↗
95. Photoinduced C(sp3)–H functionalization of glycine derivatives: preparation of unnatural α-amino acids and late-stage modification of peptides10.1021/acs.accounts.3c00260 ↗
96. Carboxylic acids as a traceless activation group for conjugate additions: a three-step synthesis of (±)-pregabalin10.1021/ja505964r ↗
97. Electrochemical oxidation enables regioselective and scalable α-C(sp3)-H acyloxylation of sulfides10.1021/jacs.1c00288 ↗
98. Acyl-CoA thioesters as chemically-reactive intermediates of carboxylic acid-containing drugs10.1007/s00044-023-03144-5 ↗