Анотація
Fluorine-containing heterocycles play a crucial role in the pharmaceutical, agrochemical, and materials industries. The pursuit of effective and sustainable synthesis methods has driven the development of electrochemistry as a compelling alternative to conventional chemical transformations. Among these approaches, electrochemistry has emerged as a particularly promising technique for orchestrating multibond-forming processes under mild, environmentally benign conditions. This review highlights key advances over the past decade in the electrochemical synthesis of fluorinated heterocyclic compounds, encompassing bimolecular, trimolecular, and tetramolecular reactions. Emphasis is placed on multicomponent cascade strategies, radical-mediated couplings, and oxidant-free cyclizations that afford broad functional group tolerance and fluorine incorporation flexibility. Collectively, this work serves as a resource for researchers developing next-generation sustainable synthetic platforms tailored to fluorinated heterocycles with diverse structural and biological profiles.
Посилання
Glasstone S. An introduction to electrochemistry. Read Books Ltd; 2011.
Bagotsky V.S., editor. Fundamentals of electrochemistry. John Wiley & Sons; 2005.
Rieger P.H. Electrochemistry. Springer Science & Business Media; 2012.
Rajeshwar K.I., Ibanez J.G., Swain G.M. Electrochemistry and the environment. J. Appl. Electrochem. 1994. 24(11): 1077–1091.
doi.org/10.1007/BF00241305.
Heinze J. Ultramicroelectrodes in electrochemistry. Angew. Chem. Int. Edi. Eng. 1993. 32(9): 1268–1288.
doi.org/10.1002/anie.199312681.
Ryan M.D., Bowden E.F., Chambers J.Q. Dynamic electrochemistry: methodology and application. Anal. Chem. 1994. 66(12): 360–427.
doi.org/10.1021/ac00084a015.
Horn E.J., Rosen B.R., Baran P.S. Synthetic organic electrochemistry: an enabling and innately sustainable method. ACS Cent. Scien.
2(5): 302–308.
doi.org/10.1021/acscentsci.6b00091.
Jiang Y., Xu K., Zeng C. Use of electrochemistry in the synthesis of heterocyclic structures. Chem. Rev. 2017. 118(9): 4485–4540.
doi.org/10.1021/acs.chemrev.7b00271.
He J., Zhou X., Mei H. et al. Electrochemical reaction of indole-tethered alkynes enabling stereoselective synthesis of iodovinyl spiroindolenine-cyclopentanes. Chem. Commun. 2025. 61(41): 7454–7457.
DOI: 10.1039/D5CC01342A.
Wang N., Xu J., Mei H. et al. Electrochemical Approaches for Preparation of Tailor-Made Amino Acids, Chin. J. Org. Chem. 2021. 41: 3034–3049.
DOI: 10.6023/cjoc202102043.
Sequeira C.A., Santos D.M. Electrochemical routes for industrial synthesis. J. Braz. Chem. Soc. 2009. 20: 387–406.
doi.org/10.1590/S0103-50532009000300002.
Li G.R., Xu H., Lu X.F. et al. Electrochemical synthesis of nanostructured materials for electrochemical energy conversion and storage. Nanoscale. 2013. 5(10): 4056–4069.
doi.org/10.1039/C3NR00607G.
Schotten C., Nicholls T.P., Bourne R.A. et al. Making electrochemistry easily accessible to the synthetic chemist. Green Chem. 2020. 22(11): 3358–3375.
DOI: 10.1039/D0GC01247E.
Sbei N., Listratova A.V., Titov A.A., Voskressensky LG. Recent advances in electrochemistry for the synthesis of N-heterocycles. Synthesis. 2019. 51(12): 2455–2473.
DOI: 10.1055/s-0037-1611797.
Jing Q., Moeller K.D. From molecules to molecular surfaces. Exploiting the interplay between organic synthesis and electrochemistry. Acc. Chem. Res. 2019. 53(1): 135–143.
doi.org/10.1021/acs.accounts.9b00578.
Devi S., Wadhwa D., Sindhu J. Electro-organic synthesis: an environmentally benign alternative for heterocycle synthesis. Org. Biomol. Chem. 2022. 20(26): 5163–5229.
doi.org/10.1039/D2OB00572G.
Chen T.L., Kim H., Pan S.Y. et al. Implementation of green chemistry principles in circular economy system towards sustainable development goals: Challenges and perspectives. Scien. Total Environ. 2020. 716: 136998.
doi.org/10.1016/j.scitotenv.2020.136998.
Liu J., Lu L., Wood D. New redox strategies in organic synthesis by means of electrochemistry and photochemistry. ACS Cent. Scien. 2020. 6(8): 1317–1340.
doi.org/10.1021/acscentsci.0c00549.
Noël T., Cao Y., Laudadio G. The fundamentals behind the use of flow reactors in electrochemistry. Acc. Chem. Res. 2019. 52(10): 2858–2869.
doi.org/10.1021/acs.accounts.9b0041.
Zhu C., Ang N.W., Meyer T.H. et al. Organic electrochemistry: molecular syntheses with potential. ACS Cent. Scien. 2021. 7(3): 415–431.
doi.org/10.1021/acscentsci.0c01532.
Malapit C.A., Prater M.B., Cabrera-Pardo J.R. et al. Advances on the merger of electrochemistry and transition metal catalysis for organic synthesis. Chem. Rev. 2021. 122(3): 3180–3218.
doi.org/10.1021/acs.chemrev.1c00614.
Han J., Konno H., Sato T., Soloshonok V.A., Izawa K. Tailor-made amino acids in the design of small-molecule blockbuster drugs. Eur. J. Med. Chem. 2021. 220: 113448.
doi: 10.1016/j.ejmech.2021.113448.
Mei H., Han J., White S. et al. Tailor-made amino acids and fluorinated motifs as prominent traits in modern pharmaceuticals. Chem.—Eur. J. 2020. 26(50): 11349–11390.
doi: 10.1002/chem.202000617.
Han J., Konno H., Sato T. et al. Peptidomimetics and Peptide-Based Blockbuster Drugs. Curr. Org. Chem. 2021. 25(14): 1627–1658.
doi: 10.2174/1385272825666210610155047.
Liu J., Han J., Izawa K. et al. Cyclic tailor-made amino acids in the design of modern pharmaceuticals. Eur. J. Med. Chem. 2020. 208: 112736.
doi: 10.1016/j.ejmech.2020.112736.
Zhu Y, Han J, Wang J. et al. Modern approaches for asymmetric construction of carbon–fluorine quaternary stereogenic centers: synthetic challenges and pharmaceutical needs. Chem. Rev. 2018. 118(7): 3887–3964.
doi.org/10.1021/acs.chemrev.7b00778.
Zhu W., Wang J., Wang S. et al. Recent advances in the trifluoromethylation methodology and new CF3-containing drugs. J. Fluor. Chem. 2014. 167: 37–54.
doi.org/10.1016/j.jfluchem.2014.06.026.
Du Y., Semghouli A., Wang Q. et al. FDA‐approved drugs featuring macrocycles or medium‐sized rings. Arch. Pharm. 2025. 358(1): e2400890.
doi.org/10.1002/ardp.202400890.
Wang Q., Han J., Sorochinsky A. et al. The Latest FDA-Approved Pharmaceuticals Containing Fragments of Tailor-Made Amino Acids and Fluorine. Pharmaceuticals. 2022. 15(8): 999.
doi.org/10.3390/ ph150809991847558.
Han J., Wzorek A. Dhawan G. et al. New drugs on the pharmaceutical market containing fluorine and residues of tailor-made amino acids. Ukr. Chem. J. 2024. 90(9): 31–56.
doi: 10.33609/2708-129X.90.9.2024.31-56.
Yin Z., Hu W., Zhang W. et al. Tailor-made amino acid-derived pharmaceuticals approved by the FDA in 2019. Amino Acids. 2020. 52(9): 1227–1261.
doi: 10.1007/s00726-020-02887-4.
Liu A., Han J., Nakano A. et al. New pharmaceuticals approved by FDA in 2020: Small-molecule drugs derived from amino acids and related compounds. Chirality. 2022. 34(1): 86–103.
doi: 10.1002/chir.23376.
Wang N., Mei H., Dhawan G. et al. New Approved Drugs Appearing in the Pharmaceutical Market in 2022, Featuring Fragments of Tailor-Made Amino Acids and Fluorine. Molecules. 2023. 28(9): 3651.
doi: 10.3390/molecules28093651.
Han J., Wzorek A., Dhawan G. et al. New drugs appearing on the market in 2023: molecules containing fluorine and fragments of tailor-made amino acids. Ukr. Bioorg. Acta. 2024. 19(1): 3–20.
doi: 10.15407/bioorganica2024.01.003.
Alicja Wzorek, Jianlin Han, Taizo Ono, Karel D. Klika, Daniel Baecker, Wei Zhang, Vadim A. Soloshonok. Synthesis of Tailor-Made Amino Acids Containing C(sp2)–F bonds. Ukr. Chem. J. 2025. 91(8): 36–64.
Alicja Wzorek, Jianlin Han, Taizo Ono, Karel D. Klika, Daniel Baecker, Wei Zhang, Vadim A. Soloshonok, Cutting-Edge Strategies in the Asymmetric Synthesis of α-Aminocyclopropyl Carboxylic Acids: Essential Scaffolds for Drug Discovery. Ukr. Chem. J. 2025. 91(10): 27–71.
doi: 10.33609/2708-129X.91.10.2025.27-71
Han J., Remete A.M., Dobson L.S. et al. Next generation organofluorine containing blockbuster drugs. J. Fluor. Chem. 2020. 239: 109639.
doi.org/10.1016/j.jfluchem.2020.109639.
Mei H., Han J., Fustero S. et al. Fluorine‐Containing Drugs Approved by the FDA in 2018. Chem.—Eur. J. 2019. 25(51): 11797–11819.
doi: 10.1002/chem.201901840.
Wang Q., Bian Y., Dhawan G. et al. FDA approved fluorine-containing drugs in 2023. Chin. Chem. Lett. 2024. 35(11): 109780.
doi: 10.1016/j.cclet.2024.109780.
Mei H., Remete A.M., Zou Y. et al. Fluorine-containing drugs approved by the FDA in 2019. Chin. Chem. Lett. 2020. 31(9): 2401–2413.
doi: 10.1016/j.cclet.2020.03.050.
Yu Y., Liu A., Dhawan G. et al. Fluorine-containing pharmaceuticals approved by the FDA in 2020: Synthesis and biological activity. Chin. Chem. Lett. 2021. 32(11): 3342–3354.
doi: 10.1016/j.cclet.2021.05.042.
He J., Li Z., Dhawan G. et al. Fluorine-containing drugs approved by the FDA in 2021. Chin. Chem. Lett. 2023. 34(1): 107578.
doi: 10.1016/j.cclet.2022.06.001.
Du Y., Bian Y., Baecker D. et al. Fluorine in the Pharmaceutical Industry: FDA‐Approved Fluorine‐Containing Drugs in 2024. Chem.—Eur. J. 2025. e202500662.
doi.org/10.1002/chem.202500662.
Jianlin Han, Alicja Wzorek, Taizo Ono, Karel D. Klika, Vadim A. Soloshonok. Modern pharmaceutical drugs featuring aliphatic fluorine-containing groups. Ukr. Chem. J. 2025. 91(6): 15–54.
Han J., Wzorek A., Dhawan G. et al. Chiral, fluorine-containing pharmaceuticals. Ukr. Chem. J. 2025. 91(2): 55–90.
doi.org/10.33609/2708-129X.91.2.2025.55-90.
Ellis T.K., Hochla V.M., Soloshonok V.A. Efficient synthesis of 2-aminoindane-2-carboxylic acid via dialkylation of nucleophilic glycine equivalent. J. Org. Chem. 2003. 68(12): 4973–4976.
doi.org/10.1021/jo030065v.
Wzorek A., Sorochinsky A.E., Klika K.D. et al. Asymmetric synthesis of chi-constrained glutamic acids and related compounds via Michael addition reactions. Ukr. Chem. J. 2024. 90(8): 83–108.
doi: 10.33609/2708-129X.90.8.2024.83-108.
Han J., Liu H., Wang J. et al. Hamari’s contribution to the asymmetric synthesis of tailor-made amino acids. Ukr. Chem. J. 2024. 90(10): 88–134.
doi: 10.33609/2708-129X.90.10.2024.88-134.
Cai C., Soloshonok V.A., Hruby V.J. Michael Addition Reactions between Chiral Ni(II) Complex of Glycine and 3-(trans-Enoyl)oxazolidin-2-ones. A Case of Electron Donor–Acceptor Attractive Interaction-Controlled Face Diastereoselectivity. J. Org. Chem. 2001. 66(4): 1339–1350.
doi: 10.1021/jo0014865.
Soloshonok V.A., Kirilenko A.G., Fokina N.A. et al. Biocatalytic resolution of β-fluoroalkyl-β-amino acids. Tetrahedron: Asymmetry. 1994. 5(6): 1119–1126.
doi.org/10.1016/0957-4166(94)80063-4.
Bravo P., Farina A., Kukhar V.P et al. Stereoselective additions of α-lithiated alkyl-p-tolylsulfoxides to N-PMP (fluoroalkyl) aldimines. An efficient approach to enantiomerically pure fluoro amino compounds. J. Org. Chem. 1997. 62(11): 3424–3425.
doi.org/10.1021/jo970004v.
Turcheniuk K.V., Poliashko K.O., Kukhar V.P. et al. Efficient asymmetric synthesis of trifluoromethylated β-aminophosphonates and their incorporation into dipeptides. Chem. Commun. 2012. 48(94): 11519–11521.
DOI: 10.1039/c2cc36702e.
Cherednichenko A.S., Rassukana Y.V. Recent advances in the asymmetric functionalization of N-(tert-butylsulfinyl) polyfluoroalkyl imines. J. Org. Pharmaceut. Chem. 2025. 23(2): 3–22.
doi.org/10.24959/ophcj.25.321224.
Qiu W., Gu X., Soloshonok V.A. et al. Stereoselective synthesis of conformationally constrained reverse turn dipeptide mimetics. Tetrahedron Lett. 2001. 42(2): 145–148.
doi: 10.1016/S0040-4039(00)01864-5.
Soloshonok V.A., Ono T. The effect of substituents on the feasibility of azomethine-azomethine isomerization: new synthetic opportunities for biomimetic transamination. Tetrahedron. 1996. 52(47): 14701–14712.
doi.org/10.1016/0040-4020(96)00920-9.
Ellis T.K., Martin C.H., Tsai G.M. et al. Efficient synthesis of sterically constrained symmetrically α,α-disubstituted α-amino acids under operationally convenient conditions. J. Org. Chem. 2003. 68(16): 6208–6214.
doi.org/10.1021/jo030075w.
Soloshonok V.A., Cai C., Hruby V.J. Asymmetric Michael addition reactions of chiral Ni (II)-complex of glycine with (N-trans-enoyl) oxazolidines: improved reactivity and stereochemical outcome. Tetrahedron: Asymmetry. 1999. 10(22): 4265–4269.
doi.org/10.1016/S0957-4166(99)00483-8.
Rizzo C., Amata S., Pibiri I. et al. FDA-approved fluorinated heterocyclic drugs from 2016 to 2022. Int. J. Mol. Sci. 2023. 24(9): 7728.
doi.org/10.3390/ijms24097728.
He J., Wang C., Mei H. et al. Visible-light-promoted cyclization of 3-indolylallylamides enabling synthesis of tetrahydrocarbolinones. Tetrahedron. 2024. 150: 133776.
doi.org/10.1016/j.tet.2023.133776.
Du Y., Mei H., Makarem A. et al. Copper-catalyzed multicomponent reaction of β-trifluoromethyl β-diazo esters enabling the synthesis of β-trifluoromethyl N,N-diacyl-β-amino esters. Beilstein J. Org. Chem. 2024. 20(1): 212–219.
doi.org/10.3762/bjoc.20.21.
Javahershenas R., Mei H., Koley M. et al. Recent advances in the multicomponent synthesis of heterocycles using 5-aminotetrazole. Synthesis. 2024. 56(16): 2445–2461.
doi: 10.1055/s-0042-1751526.
Abbas A.A., Farghaly T.A., Dawood K.M. Recent progress in therapeutic applications of fluorinated five-membered heterocycles and their benzo-fused systems. RSC Adv. 2024. 14(46): 33864–33905.
doi: 10.1039/D4RA05697C.
Yamada T., Okada T., Sakaguchi K. et al. Efficient asymmetric synthesis of novel 4-substituted and configurationally stable analogues of thalidomide. Org. Lett. 2006. 8(24): 5625–5628.
doi: 10.1021/ol0623668.
Takeda R., Kawamura A., Kawashima A. et al. Chemical dynamic kinetic resolution and S/R interconversion of unprotected α‐amino acids. Angew. Chem., Int. Ed. 2014. 53(45): 12214–12217.
doi.org/10.1002/anie.201407944.
Wang Y., Song X., Wang J. et al. Recent approaches for asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes. Amino Acids. 2017. 49(9): 1487–1520.
doi: 10.1007/s00726-017-2458-6.
Nian Y., Wang J., Zhou S. et al. Recyclable ligands for the non‐enzymatic dynamic kinetic resolution of challenging α‐amino acids. Angew. Chem., Int. Ed. 2015. 54(44): 12918–12922.
doi.org/10.1002/anie.201507273.
Grygorenko O.O., Volochnyuk D.M., Vashchenko B.V. Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances. Eur. J. Org. Chem. 2021. (47): 6478–6510.
doi.org/10.1002/ejoc.202100857.
Leśniewska A., Przybylski P. Seven-membered N-heterocycles as approved drugs and promising leads in medicinal chemistry as well as the metal-free domino access to their scaffolds. Eur. J. Med. Chem. 2024. 275: 116556.
doi.org/10.1016/j.ejmech.2024.116556.
Kumar N., Goel N. Heterocyclic compounds: importance in anticancer drug discovery. Anticancer Agents Med. Chem. 2022. 22(19): 3196–3207.
doi.org/10.2174/1871520622666220404082648.
Rusu A., Moga I.M., Uncu L., Hancu G. The role of five-membered heterocycles in the molecular structure of antibacterial drugs used in therapy. Pharmaceutics. 2023. 15(11): 2554.
doi.org/10.3390/pharmaceutics15112554.
Al‐Bogami A.S., Saleh T.S., Moussa T.A. Green synthesis, antimicrobial activity and cytotoxicity of novel fused pyrimidine derivatives possessing a trifluoromethyl moiety. ChemistrySelect. 2018. 3(28): 8306–8311.
doi.org/10.1002/slct.201801050.
Soloshonok V.A., Mikami K., Yamazaki T., Welch J.T., Honek J.F. Eds. Current fluoroorganic chemistry: new synthetic directions, technologies, materials, and biological applications. ACS Symposium Series #949; Oxford University Press, 2007.
doi: 10.1021/bk-2007-0949.
Lyutenko N.V., Han J., Wzorek A. et al. Carbon nanotubes-catalyzed synthesis of fluorine-containing heterocycles. Ukr. Chem. J. 2024. 90(6): 71–86.
doi: 10.33609/2708-129X.90.6.2024.71-86.
Jianlin Han, Alicja Wzorek, Taizo Ono, Karel D. Klika, Vadim A. Soloshonok, Mechanochemical Synthesis of Fluorine-Containing Heterocycles via Ball Milling. Ukr. Chem. J., 2025. 91(7): 35–55.
Yang Z., Zhang J., Hu L. et al. Electrochemical HI-mediated Intermolecular C–N Bond Formation to Synthesize Imidazoles from Aryl Ketones and Benzylamines. J. Org. Chem. 2020. 85(9): 5952–5958.
doi.org/10.1021/acs.joc.0c00316.
Soloshonok V.A., Hayashi T., Ishikawa K., Nagashima N. Highly diastereoselective aldol reaction of fluoroalkyl aryl ketones with methyl isocyanoacetate catalyzed by silver (I)/triethylamine. Tetrahedron Lett. 1994. 35(7): 1055–1058.
doi.org/10.1016/S0040-4039(00)79964-3.
Soloshonok V.A., Kacharov A.D., Avilov D.V. et al. Transition Metal/Base-Catalyzed Aldol Reactions of Isocyanoacetic Acid Derivatives with Prochiral Ketones, a Straightforward Approach to Stereochemically Defined β, β-Disubstituted-β-hydroxy-α-amino Acids. 1 Scope and Limitations. J. Org. Chem. 1997. 62(11): 3470–3479.
doi.org/10.1021/jo9623402.
Elinson M.N., Dorofeeva E.O., Vereshchagin A.N. et al. Electrocatalytic stereoselective transformation of aldehydes and two molecules of pyrazolin-5-one into (R*, R*)-bis-(spiro-2, 4-dihydro-3 H-pyrazol-3-one) cyclopropanes. Cat. Scien. Technol. 2015. 5(4): 2384–2387.
doi.org/10.1039/C4CY01681E.
Qian P., Jiang S., Fan H. et al. Electrochemically Enabled Cascade Cyclization Reaction of Aromatic Aldehydes and Pyrazol-5-amines: Synthesis of Bis-pyrazolo [3,4-b:4′,3′-e] pyridines. J. Org. Chem. 2022. 87(14): 9242–9249.
doi.org/10.1021/acs.joc.2c00988.
Soloshonok V.A., Hayashi T. Gold(I)-catalyzed asymmetric aldol reaction of fluorinated benzaldehydes with α-isocyanoacetamide. Tetrahedron: Asymmetry. 1994. 5(6): 1091–1094.
doi: 10.1016/0957-4166(94)80059-6.
Soloshonok V.A., Hayashi T. Gold(I)-catalyzed asymmetric aldol reaction of methyl isocyanoacetate with fluorinated benzaldehydes. Tetrahedron Lett. 1994. 35(17): 2713–2716.
doi: 10.1016/S0040-4039(00)77013-4.
Mohammadi A.A., Makarem S., Ahdenov R., Notash N.A. Green pseudo-multicomponent synthesis of some new spirocyclopropane derivatives via electro-catalyzed reaction. Mol. Diversity. 2020. 24: 763–770.
doi.org/10.1007/s11030-019-09979-8.
Zhang X., Zhao L., Liang Y.Y. et al. Electrochemical Synthesis of PhSe/CF3-containing Dibenzazepines via Radical Cascade Cyclization of Alkynes. Chem. Commun. 2025.
doi.org/10.1039/D5CC02355F.
Qian X., Qing-Xiao T., Jian-Ji Z. Recent Progress on the Synthesis of Benzazepine Derivatives via Radical Cascade Cyclization Reactions. Chin. J. Org. Chem. 2022. 42(12): 3979.
DOI: 10.6023/cjoc202209025.
Gao X., Wang P., Wang Q. et al. Electrochemical oxidative annulation of amines and aldehydes or ketones to synthesize polysubstituted pyrroles. Green Chem. 2019. 21(18): 4941–4945.
DOI: 10.1039/C9GC02118C
Kong W.J., Shen Z., Finger L.H, Ackermann L. Electrochemical access to aza‐polycyclic aromatic hydrocarbons: Rhoda‐electrocatalyzed domino alkyne annulations. Angew. Chem. Int. Ed. 2020. 59(14): 5551–5556.
doi.org/10.1002/anie.201914775.
Zhang Y., Xu S., Zhu Y. et al. One‐pot synthesis of 4‐thiocyanato‐1H‐pyrazoles through electrochemical multicomponent thiocyanation under metal‐and oxidant‐free conditions. Eur. J. Org. Chem. 2023. 26(2): e202201278.
doi.org/10.1002/ejoc.202201278.
Elinnson M.N., Ryzkova Y.E., Vereschagin A.N. et al. Electrochemically induced assembling of isatins, kojic acid, and malonic acid derivatives into substituted spiro [indole‐3, 4′‐pyran]‐2 (1 H)‐one scaffold and predicting potential protein targets. J. Heterocyc. Chem. 2022. 56(2): 277–299.
doi.org/10.11002/jhet.4579.
Elinson M.N., Ryzkova Y.E., Ryzkov F.V. et al. Electrochemically Induced Facile and Efficient Multicomponent Approach to Medicinally Relevant 4‐[4‐oxo‐4H‐pyran‐2‐yl](aryl)‐methylisoxazol‐5 (2H)‐one Scaffold. ChemistrySelect. 2020. 5(20): 5981–5986.
doi.org/10.1002/slct.2002001592.
Soloshonok V.A., Avilov D.V., Kukhar V.P. Highly diastereoselective asymmetric aldol reactions of chiral Ni (II)-complex of glycine with alkyl trifluoromethyl ketones. Tetrahedron: Asymmetry. 1996. 7(6): 1547–1550.
doi.org/10.1016/0957-4166(96)00177-2.
Soloshonok V.A., Avilov D.V., Kukhar V.P. Asymmetric aldol reactions of trifluoromethyl ketones with a chiral Ni (II) complex of glycine: stereocontrolling effect of the trifluoromethyl group. Tetrahedron. 1996. 52(38): 12433–12442.
doi.org/10.1016/0040-4020(96)00741-7.
Ryzkova YE, Elinson MN, Vereshchagin AN, Karpenko KA, Ryzhkov FV, Ushakov IE, Egorov MP. Multicomponent electrocatalytic selective approach to unsymmetrical spiro [Furo [3, 2-c] Pyran-2, 5′-Pyrimidine] scaffold under a column chromatography-free protocol at room temperature. Chemistry. 2022 Jun 19; 4(2): 61–529.
doi.org/10.3390/chemistry4020044.
Kumar D., Sharma S., Kalra S. et al. Medicinal perspective of indole derivatives: recent developments and structure-activity relationship studies. Curr. Drug Targets. 2020. 21(9): 864–891.
doi.org/10.2174/13894501216662003101115327.
Mo X., Rao D.P., Kaur K. et al. Indole derivatives: a versatile scaffold in modern drug discovery–an updated review on their multifaceted therapeutic applications (2020–2024). Molecules. 2024. 29(19): 4770.
doi.org/10.3390/molecules29194770.
Kaushik N.K., Kaushik N., Attri P. et al. Biomedical importance of indoles. Molecules. 2013. 18(6): 6620–6662.
doi.org/10.3390/molecules18066620.
Kumar S., Ritika. A brief review of the biological potential of indole derivatives. Future J. Pharm. Sci. 2020. 1–9.
doi.org/10.1186/s43094-020-00141-y.
Xie C, Mei H, Wu L, Soloshonok VA, Han J, Pan Y. LDA-promoted asymmetric synthesis of β-trifluoromethyl-β-amino indanone derivatives with virtually complete stereochemical outcome. RSC Adv. 2014. 4(9): 4763–4768.
DOI: 10.1039/C3RA45773G.
Taber D.F., Tirunahari P.K. Indole synthesis: a review and proposed classification. Tetrahedron. 2011. 67(38): 7195–7210.
doi.org/10.1016/j.tet.2011.06.040.
Gribble G.W. Recent developments in indole ring synthesis–Methodology and applications. Contemp. Org. Synth. 1994. 1(3): 145–172.
doi: 10.1039/CO9940100145.
Wu L., Xie C., Mei H. et al. Asymmetric Friedel–Crafts Reactions of N-tert-Butylsulfinyl-3,3,3-trifluoroacetaldimines: General
Access to Enantiomerically Pure Indoles Containing a 1-Amino-2,2,2-trifluoroethyl Group. J. Org. Chem. 2014. 79(16): 7677–7681.
doi.org/10.1021/jo5012009.
Zhu Y., Mao Y., Mei H. et al. Palladium‐Catalyzed Asymmetric Allylic Alkylations of Colby Pro‐Enolates with MBH Carbonates: Enantioselective Access to Quaternary C–F Oxindoles. Chem.—Eur. J. 2018. 24(36): 8994–8998.
doi.org/10.1002/chem.201801670.
Li T., Zhou S., Wang J. et al. Asymmetric synthesis of α-(1-oxoisoindolin-3-yl)glycine: synthetic and mechanistic challenges. Chem. Commun. 2015 51(9): 1624–1626;
doi: 10.1039/C4CC05659K.
Xie C., Zhang L., Sha W. et al. Detrifluoroacetylative in situ generation of free 3-fluoroindolin-2-one-derived tertiary enolates: design, synthesis, and assessment of reactivity toward asymmetric Mannich reactions. Org. Lett. 2016. 18(13): 3270–3273.
doi.org/10.1021/acs.orglett.6b01516.
Zhang L., Zhang W., Mei H. et al. Catalytic asymmetric aldol addition reactions of 3-fluoro-indolinone derived enolates. Org. Biomolec. Chem. 2017. 15(2): 311–315.
doi.org/10.1039/C6OB02454H.
Singh V.K., Dubey R., Upadhyay A. et al. Electrochemical approach for synthesis of 3-substituted indole derivatives. Tetrahedron Lett. 2017. 58(45): 4227–4231.
doi.org/10.1016/j.tetlet.2017.09.003.
Soloshonok V.A., Kacharov A.D., Hayashi T. Gold (I)-catalyzed asymmetric aldol reactions of isocyanoacetic acid derivatives with fluoroaryl aldehydes. Tetrahedron. 1996. 52(1): 245–254.
doi.org/10.1016/0040-4020(95)00893-D.
Ono T., Kukhar V.P., Soloshonok V.A. Biomimetic reductive amination of fluoro aldehydes and ketones via [1, 3]-proton shift reaction. 1 scope and limitations. J. Org. Chem. 1996. 61(19): 6563–6569.
doi.org/10.1021/jo960503g.
Matin M.M., Matin P., Rahman M.R. et al. Triazoles and their derivatives: Chemistry, synthesis, and therapeutic applications. Front. Molec. Bioscien. 2022. 9: 864286.
doi.org/10.3389/fmolb.2022.864286.
Mei H., Xiong Y., Xie C. et al. Concise and scalable asymmetric synthesis of 5-(1-amino-2,2,2-trifluoroethyl) thiazolo [3,2-b][1,2,4] triazoles. Org. Biomolec. Chem. 2014. 12(13): 2108–2113.
DOI: 10.1039/C3OB42348D.
Zhao Z., He Y., Li M. et al. An electrochemical multicomponent [3+1+1] annulations to synthesize polysubstituted 1,2,4-triazoles. Tetrahedron. 2021. 87: 132111.
doi.org/10.1016/j.tet.2021.132111.
Kabi A.K., Gujjarappa R., Singh V., Malakar C.C. Biological impacts of imidazoline derivatives. Chem. Papers. 2024. 78(10): 5743–5752.
doi.org/10.1007/s11696-024-03496-1.
Mei H., Xie C., Wu L. et al. Asymmetric Mannich reactions of imidazo [2,1-b] thiazole-derived nucleophiles with (SS)-N-tert-butanesulfinyl (3,3,3)-trifluoroacetaldimine. Org. Biomolec. Chem. 2013. 11(46): 8018–8021.
DOI: 10.1039/c3ob41785a.
Saney L., Panduwawala T., Li X. et al. Synthesis of fused tetramate-oxazolidine and-imidazolidine derivatives and their antibacterial activity. Org. Biomolec. Chem. 2023. 21(23): 4801–4809.
doi.org/10.1039/D3OB00594A.
Soloshonok V.A., Ueki H., Jiang C. et al. A Convenient, Room‐Temperature–Organic Base Protocol for Preparing Chiral 3‐(Enoyl)‐1,3‐oxazolidin‐2‐ones. Helv. Chim. Acta. 2002. 85(11): 3616–3623.
doi.org/10.1002/1522-2675(200211)85: 11<3616::AID-HLCA3616>3.0.CO;2-O.
Claraz A., Djian A., Masson G. Electrochemical tandem trifluoromethylation of allylamines/formal (3+2)-cycloaddition for the rapid access to CF3-containing imidazolines and oxazolidines. Org. Chem. Front. 2021. 8(2): 288–296.
DOI: 10.1039/D0QO01307B.
Lalezari I., Shafiee A., Yalpani M. Selenium-Nitrogen Heterocycles. Adv. Heterocyc. Chem. 1979. 24: 109–150.
doi.org/10.1016/S0065-2725(08)60509-7.
Soloshonok V.A., Nelson D.J. Alkene selenenylation: A comprehensive analysis of relative reactivities, stereochemistry and asymmetric induction, and their comparisons with sulfenylation. Beilstein J. Org. Chem. 2011. 7(1): 744–758.
doi.org/10.3762/bjoc.7.85.
Wu Y., Chen J.Y., Ning J. et al. Electrochemical multicomponent synthesis of 4-selanylpyrazoles under catalyst-and chemical-oxidant-free conditions. Green Chem. 2021. 23(11): 3950–3954.
DOI: 10.1039/d1gc00562f.
Siyu M., Hongxia L., Zhilin W. et al. Electrocatalytic three-component synthesis of 4-bromopyrazoles from acetylacetone, hydrazine and diethyl bromomalonate. Chin. J. Org. Chem. 2022. 42(12): 4292.
DOI: 10.6023/cjoc202211002.
Ohkura H., Berbasov D.O., Soloshonok V.A. Chemo-and regioselectivity in the reactions between highly electrophilic fluorine containing dicarbonyl compounds and amines. Improved synthesis of the corresponding imines/enamines. Tetrahedron. 2003. 59(10): 1647–1656.
doi.org/10.1016/S0040-4020(03)00138-8.
Bravo P., Guidetti M., Viani F. et al. Chiral sulfoxide controlled asymmetric additions to C N double bond. An efficient approach to stereochemically defined α-fluoroalkyl amino compounds. Tetrahedron. 1998. 54(42): 12789–12806.
doi: 10.1016/S0040-4020(98)00779-0.
Shibata N., Nishimine T., Shibata N. et al. Organic base-catalyzed stereodivergent synthesis of (R)- and (S)-3-amino-4,4,4-trifluorobutanoic acids. Chem. Commun. 2012. 48: 4124–4126.
doi:10.1039/C2CC30627A.
Soloshonok V.A., Kirilenko A.G., Kukhar V.P., Resnati G. Transamination of fluorinated β-keto carboxylic esters. A biomimetic approach to β-polyfluoroalkyl-β-amino acids. Tetrahedron Lett. 1993. 34(22): 3621–3624.
doi.org/10.1016/S0040-4039(00)73652-5.
Makarem S., Fakhari A.R., Mohammadi A.A. Electro-organic synthesis of nanosized particles of 3-hydroxy-3-(1H-indol-3-yl) indolin-2-one derivatives. Monat. Chem. 2012. 143: 1157–1160.
doi.org/10.1007/s00706-011-0693-1.
He W.B., Zhao S.J., Chen J.Y. et al. External electrolyte-free electrochemical one-pot cascade synthesis of 4-thiocyanato-1H-pyrazoles. Chin. Chem. Lett. 2023. 34(2): 107640.
doi.org/10.1016/j.cclet.2022.06.063.
Torchinsky Y.M. Transamination: its discovery, biological and chemical aspects (1937–1987). Trends Biochem. Scien. 1987. 12: 115–117.
doi.org/10.1016/0968-0004(87)90052-1.
Wzorek A., Han J., Lyutenko N.V. et al. Discovery of biomimetic transamination as a general synthetic method for preparation of fluorine-containing amines and amino acids. Ukr. Bioorg. Acta. 2023. 18(2): 3–15.
DOI: doi.org/10.15407/bioorganica2023.02. 003.
Fuchs M., Farnberger J.E., Kroutil W. The industrial age of biocatalytic transamination. Eur. J. Org. Chem. 2015. (32): 6965–6982.
doi.org/10.1002/ejoc.201500852.
Xiao X., Zhao B. Vitamin B6-based biomimetic asymmetric catalysis. Acc. Chem. Res. 2023. 56(9): 1097–1117.
doi.org/10.1021/acs.accounts.3c00053.
Chen J., Liu Y.E., Gong X. et al. Biomimetic chiral pyridoxal and pyridoxamine catalysts. Chin. J. Chem. 2019. 37(2): 103–112
doi.org/10.1002/cjoc.201800478.
Yasumoto M., Ueki H., Soloshonok V.A. Thermal 1,3-proton shift reaction and its application for operationally convenient and improved synthesis of α-(trifluoromethyl) benzylamine. J. Fluor. Chem. 2007. 128(7): 736–739.
doi.org/10.1016/j.jfluchem.2007.02.008.
Soloshonok V.A., Kirilenko A.G., Kukhar V.P., Resnati G. A practical route to fluoroalkyl-and fluoroarylamines by base-catalyzed [1, 3]-proton shift reaction. Tetrahedron Lett. 1994. 35(19): 3119–3122.
doi.org/10.1016/S0040-4039(00)76845-6.
Soloshonok V.A., Yasumoto M. Catalytic asymmetric synthesis of α-(trifluoromethyl) benzylamine via cinchonidine derived base-catalyzed biomimetic 1,3-proton shift reaction. J. Fluor. Chem. 2007. 128(3): 170–173.
doi.org/10.1016/j.jfluchem.2006.11.011.
Soloshonok V.A., Ohkura H., Yasumoto M. Operationally convenient asymmetric synthesis of (S)- and (R)-3-amino-4,4,4-trifluorobutanoic acid: Part II. Enantioselective biomimetic transamination of 4,4,4-trifluoro-3-oxo-N-[(R)-1-phenylethyl)butanamide. J. Fluor. Chem. 2006. 127(7): 930–935.
doi: 10.1016/j.jfluchem.2006.04.004.
Soloshonok V.A., Ohkura H., Uneyama K. Biomimetic reductive amination of perfluoroalkylcarboxylic acids to α,α-dihydroperfluoroalkylamines. Tetrahedron Lett. 2002. 43(31): 5449–5452.
doi.org/10.1016/S0040-4039(02)01104-8.
Qian P., Zhou Z., Hu K. et al. Electrocatalytic three-component reaction: synthesis of cyanide-functionalization imidazo-fused N-heterocycles. Org. Lett. 2019. 21(16): 6403–6407. doi.org/10.1021/acs.orglett.9b02317.
Soloshonok V.A., Kukhar V.P. Biomimetic transamination of α-keto perfluorocarboxylic esters. An efficient preparative synthesis of β,β,β-trifluoroalanine. Tetrahedron. 1997. 53(25): 8307–8314.
doi.org/10.1016/S0040-4020(97)00517-6.
Soloshonok V.A., Kirilenko A.G., Fokina N.A. et al. Chemo-enzymatic approach to the synthesis of each of the four isomers of α-alkyl-β-fluoroalkyl-substituted β-amino acids. Tetrahedron: Asymmetry. 1994. 5(7): 1225–1228.
doi.org/10.1016/0957-4166(94)80163-0.
Soloshonok V.A, Kukhar V.P. Biomimetic base-catalyzed [1, 3]-proton shift reaction. A practical synthesis of β-fluoroalkyl-β-amino acids. Tetrahedron. 1996. 52(20): 6953–6964.
doi.org/10.1016/0040-4020(96)00300-6.
Yang Z., Zhang J., Hu L. et al. Electrochemical HI-mediated Intermolecular C–N Bond Formation to Synthesize Imidazoles from Aryl Ketones and Benzylamines. J. Org. Chem. 2020. 85(9): 5952–5958.
doi.org/10.1021/acs.joc.0c00316.
Soloshonok V.A., Kirilenko A.G., Galushko S.V., Kukhar V.P. Catalytic asymmetric synthesis of β-fluoroalkyl-β-amino acids via biomimetic [1,3]-proton shift reaction. Tetrahedron Lett. 1994. 35(28): 5063–5064.
doi.org/10.1016/S0040-4039(00)73320-X.
Soloshonok V.A., Ono T., Soloshonok I.V. Enantioselective biomimetic transamination of β-keto carboxylic acid derivatives. an efficient asymmetric synthesis of β-(fluoroalkyl) β-amino acids. J. Org. Chem. 1997. 62(22): 7538–7539.
doi.org/10.1021/jo9710238.
Soloshonok V.A., Soloshonok I.V., Kukhar V.P., Svedas V.K. Biomimetic transamination of α-alkyl β-keto carboxylic esters. Chemoenzymatic approach to the stereochemically defined α-alkyl β-fluoroalkyl β-amino acids. J. Org. Chem. 1998. 63(6): 1878–1884.
doi.org/10.1021/jo971777m.
Zhou K., Xia S., Liu Y., Chen Z. An electrochemical tandem Michael addition, azidation and intramolecular cyclization strategy for the synthesis of imidazole derivatives. Org. Biomolec. Chem. 2022. 20(39): 7840–7844.
doi.org/10.1039/D2OB01501C.
Asghariganjeh M.R., Mohammadi A.A., Tahanpesar E. et al. Electro-organic synthesis of tetrahydroimidazo [1,2-a]pyridin-5(1H)-one via a multicomponent reaction. Molec. Diversity. 2021. 25: 509–516.
DOI: 10.1007/s11030-019-10029-6.
You S., Ruan M., Lu C. et al. Paired electrolysis enabled annulation for the quinolyl-modification of bioactive molecules. Chem.
Scien. 2022. 13(8): 2310–2316.
doi.org/10.1039/D1SC06757E.
Jörres M., Aceña J.L., Soloshonok V.A., Bolm C. Asymmetric Carbon-Carbon Bond Formations under Solvent-Less Conditions in Ball Mills. ChemCatChem. 2015. 7: 1265–1269.
doi: 10.1002/cctc.201500102.
Zou Y., Han J., Saghyan A.S. et al. Asymmetric Synthesis of Tailor-Made Amino Acids
Using Chiral Ni(II) Complexes of Schiff Bases. An Update of the Recent Literature.
Molecules. 2020. 25(12): 2739.
doi.org/10.3390/molecules25122739.
Xie C., Wu L., Mei H. et al. Generalized access to fluorinated β-keto amino compounds through asymmetric additions of α,α-difluoroenolates to CF3-sulfinylimine. Org. Biomol. Chem. 2014. 12(39): 7836–7843.
doi: 10.1039/C4OB01575D.
Malviya B.K., Jassal A.K., Karnatak M. et al. Electro-Oxidative sp3 C–H Bond Functionalization and Annulation Cascade: Synthesis of Novel Heterocyclic Substituted Indolizines. J. Org. Chem. 2022. 87(5): 2898–2911.
doi.org/10.1021/acs.joc.1c02773.
Yang N., Yuan G. A multicomponent electrosynthesis of 1, 5-disubstituted and 1-aryl 1, 2, 4-triazoles. J. Org. Chem. 2018. 83(19): 11963–11969.
doi.org/10.1021/acs.joc.8b01808.
