Ferrocene as a leaving group; Unexpected rearrangement reactions for the synthesis of 2,3-diarylnapthoquinones

In general, Suzuki-Miyaura coupling reaction between aryl bromide and arylboronic acids formthe new C-C bond in the presence of Pd-catalyst. In the present study, 2-bromo-3-ferrocenyl1,4-naphthoquinone 2 intermediate is synthesized by starting from 2,3-dibromo-1,4-naphthoquinone via Suzuki-Miyaura Coupling reaction. Then, it is investigated that the reactionbetween 2 and arylboronic acids give a new rearrangement reaction involving free radicals.Ferrocene structure displays critical roles for the formation of 2,3-diaryl-1,4-naphthoquinones.This reaction could be first example for the radical C-C bond cleavage reactions includingferrocene.

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[1] Semwal R.B., Semwal D.K., Combrinck S., Cartwright-Jones C., Viljoen A., “Lawsonia inermis L. (henna): Ethnobotanical, phytochemical and pharmacological aspects”, Journal of Ethnopharmacology, 155, (2014), 80-103
[2] Carbas B.B., Kivrak A., Zora M., Onal A.M., “Synthesis of a novel fluorescent and ion sensitive monomer bearing quinoxaline moieties and its electropolymerization”, Reactive & Functional Polymers, 71, (2011), 579-587
[3] Devaux C.A., Rolain J-M., Colson P., Raoult D., “New insights on the antiviral effects of chloroquine against coronavirus: what to expect for COVID-19?”, International Journal of Antimicrobial Agents, 55(5), (2020),105938
[4] Abbas G., Hassan Z., Al-Harrasi A., Khan A., AlAdawi A., Ali M., “Synthesis, biological evaluation, molecular docking and structure-activity relationship studies of halogenated quinone and naphthoquinone derivatives”, Journal of Molecular Structure, 1195, (2019), 462-469
[5] Amani A M., “Synthesis, Characterization and Antibacterial and Antifungal Evaluation of Some ParaQuinone Derivatives”, Drug Research, 64(8), (2014), 420-423.
[6] Jardim G.A.M., da Cruz E.H.G., Valenca W.O., Lima D.J.B., Cavalcanti B.C., Pessoa C., Rafique J., Braga A.L., Jacob C., da Silva E.N., “Synthesis of SeleniumQuinone Hybrid Compounds with Potential Antitumor Activity via Rh-Catalyzed C-H Bond Activation and Click Reactions”, Molecules, 2018, 23.
[7] Michalik M., Poliak P., Lukes V., Klein E., “From phenols to quinones: Thermodynamics of radical scavenging activity of para-substituted phenols”, Phytochemistry, 166, (2019), 112077.
[8] Zangeneh M.M., Zangeneh A., Pirabbasi E., Moradi R., Almasi M., “Falcaria vulgaris leaf aqueous extract mediated synthesis of iron nanoparticles and their therapeutic potentials under in vitro and in vivo condition”, Applied Organometallic Chemistry, 33(12), (2019), e5246
[9] Yu N., Li X., Wen M., Geng P., Ren X.L., Wang Z.J., Chen Z.G., “Doxorubicin-Loaded Bi-PEG Nanoparticles as Novel Chemo-Photothermal Nanoagents for Efficiently Killing Cancer Cells”, Journal of Nanoscience and Nanotechnology, 20, (2020), 2032-2039
[10] Moaven O., Votanopoulos K.I., Shen P., Mansfield P., Bartlett D.L., Russell G., McQuellon R., Stewart J.H., Levine E.A., “Health-Related Quality of Life After Cytoreductive Surgery/HIPEC for Mucinous Appendiceal Cancer: Results of a Multicenter Randomized Trial Comparing Oxaliplatin and Mitomycin”, Annals of Surgical Oncology, 27, (2020), 772–780
[11] Ishikawa T., “Recent advances in pharmacogenomics of ABC transporters involved in breast cancer therapy”, Pharmacogenomics, 13, (2012), 633-636
[12] Tietze L.F., Bell H.P., Chandrasekhar S., “Natural product hybrids as new leads for drug discovery”, Angewandte Chemie-International Edition, 42, (2003), 3996-4028
[13] Fang G.D., Gao J., D. Dionysiou D., Liu C., Zhou D.M., “Activation of persulfate by quinones: free radical reactions and implication for the degradation of PCBs”, Environmental Science & Technology, 47, (2013), 4605-4611
[14] Zora M., Kivrak A., Kelgokmen Y., “A novel one-pot synthesis of ferrocenyl-substituted 1, 2, 4-oxadiazoles”, Journal of Organometallic Chemistry, 759, (2014), 67- 73.
[15] Santos M., Bastos P., Catela I., Zalewska K., Branco L.C., “Recent Advances of Metallocenes for Medicinal Chemistry”, Mini-Reviews in Medicinal Chemistry, 17, (2017), 771-784
[16] Aslan-Ertas N., Kavak E., Salma F., Celik-Kazici H., Kivrak H., Kivrak A., “Synthesis of Ferrocene Based Naphthoquinones and its Application as Novel Non‐ enzymatic Hydrogen Peroxide”, Electroanalysis, 32 (6), (2020), 1178-1185
[17] Wang X.Y., Li Q., Xu J.J., Wu S., Xiao T.F., Hao J., Yu P., Mao L.Q., “Rational Design of Bioelectrochemically Multifunctional Film with Oxidase, Ferrocene, and Graphene Oxide for Development of in Vivo Electrochemical Biosensors”, Analytical Chemistry, 88, (2016), 5885-5891.
[18] Guyon L., Lepeltier E., Gimel J.C., Calvignac B., Franconi F., Lautram N., Dupont A., Bourgaux C., Pigeon P., Saulnier P., Jaouen G., Passirani C., “Importance of Combining Advanced Particle Size Analysis Techniques To Characterize Cell-Penetrating Peptide–Ferrocifen Self-Assemblies”, Journal of Physical Chemistry Letters, 10, (2019), 6613-6620
[19] Kivrak A., Zora M., “Efficient one-pot synthesis of cyanoferrocene from ferrocenecarboxaldehyde using NH2OH· HCl/KI/ZnO/CH3CN system”, Journal of Organometallic Chemistry, 692, (2007), 2346-2349
[20] Yucel B., Sanli B., Soylemez H., Yilmaz I., “Synthesis and electro-spectroelectrochemistry of ferrocenyl naphthaquinones”, Tetrahedron, 67, (2011), 1406-1421
[21] Carbas B.B., Kivrak A., Kavak E., “Electrosynthesis of a new indole based donor-acceptor-donor type polymer and investigation of its electrochromic properties”, Materials Chemistry and Physics, 188, (2017), 68-74
[22] Sahin O., Kivrak H., Kivrak A., Kazici H.C., Alal O., Atbas D., “Facile and Rapid Synthesis of Microwave Assisted Pd Nanoparticles as Non-Enzymatic Hydrogen Peroxide Sensor”, International Journal of Electrochemical Science, 12, (2017), 762-769
[23] Hassan Z., Ullah I., Ali I., Khera R.A., Knepper I., Ali A., Patonay T., Villinger A., Langer P., “Synthesis of tetraaryl-p-benzoquinones and 2,3-diaryl-1,4- naphthoquinones via Suzuki-Miyaura cross-coupling reactions”, Tetrahedron, 69, (2013), 460-469
[24] Cho C.H., Jung D.I., Neuenswander B., Larock R.C., “Parallel Synthesis of a Desketoraloxifene Analogue Library via Iodocyclization/Palladium-Catalyzed Coupling”, Acs Combinatorial Science, 13, (2011), 501-510
[25] Algso M.A.S., Kivrak A., “New strategy for the synthesis of 3-ethynyl-2-(thiophen-2-yl) benzo [b] thiophene derivatives”, Chemical Papers, 73, (2019), 977-985
[26] Yoshida S., Kubo H., Saika T., Katsumura S., “Synthesis of 2,3-Diarylquinone by Palladium Catalyzed Cross-Coupling of Dibromoquinones with Heteroarylstannanes”, Chemistry Letters, (1996), 139- 140.
[27] Best W.M., Sims C.G., Winslade M., “PalladiumCatalysed Cross Coupling of Arylboronic Acids with 2- Chloro-1,4-naphthoquinones: The Synthesis of 2-Aryland 2,3-Bisaryl-1,4-naphthoquinones”, Australian Journal of Chemistry, 54, (2001), 401-404
[28] Davies M.W., Johnson C.N., Harrity J.P.A., “Synthesis of Novel Quinone Boronic Ester Derivatives via a Highly Regioselective Cr-Mediated Benzannulation Reaction and Their Application in Pd-Catalyzed Coupling Processes”, Journal of Organic Chemistry, 66, (2001), 3525-3532
[29] Hsung R.P., Xu Y.C., Wulff W.D., “The Effects of Phosphine Ligands on the Benzannulation Reaction of Molybdenum Carbene Complexes with Alkynes”, Tetrahedron Letters, 36, (1995), 8159-8162
[30] Patil P., Nimonkar A., Akamanchi K.G., “Aryl-Free Radical-Mediated Oxidative Arylation of Naphthoquinones Using o-Iodoxybenzoic Acid and Phenylhydrazines and Its Application toward the Synthesis of Benzocarbazoledione”, Journal of Organic Chemistry, 79, (2014), 2331-2336
[31] Fujiwara Y., Domingo V., Seiple I.B., Gianatassio R., Del Bel M., Baran P.S., “Practical C−H Functionalization of Quinones with Boronic Acids”, Journal of the American Chemical Society, 133, (2011), 3292-3295
[32] Wang J., Wang S., Wang G., Zhang J., Yu X.Q., “Ironmediated direct arylation with arylboronic acids through an aryl radical transfer pathway”, Chemical Communications, 48, (2012), 11769-11771
[33] Komeyama K., Kashihara T., Takaki K., “FeSO4- promoted direct arylation of benzoquinones with ArB(OH)2 or ArBF3K”, Tetrahedron Letters, 54, (2013), 1084-1086
[34] Wang Y.J., Zhu S., Zou L.H., “Recent Advances in Direct Functionalization of Quinones”, European Journal of Organic Chemistry, (2019), 2179-2201
[35] Ilangovan A., Polu A., Satish G., “K2S2O8-mediated metal-free direct C–H functionalization of quinones using arylboronic acids”, Organic Chemistry Frontiers, 2, (2015), 1616-1620