Synthetic strategy toward furyl- and benzofuryl-containing building blocks for organic materials published by Ural Federal University eISSN 2411-1414; chimicatechnoacta.ru ARTICLE 2022, vol. 9(4), No. 20229403 DOI: 10.15826/chimtech.2022.9.4.03 1 of 6 Synthetic strategy toward furyl- and benzofuryl-containing building blocks for organic materials Diana A. Eshmemet’eva İD , Danil K. Vshivkov İD , Yury A. Vasev İD , Danil A. Myasnikov* İD Perm State University, Perm 614990, Russia * Corresponding author: mda@psu.ru This paper belongs to a Regular Issue. © 2022, the Authors. This article is published in open access under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). Abstract A synthetic approach to furyl- and benzofuryl-containing building blocks utilizing easily accessible substrates is reported. Cascade acid- catalyzed reactions of 2-methylfuran with α,β-unsaturated carbonyl compounds or salicyl alcohols followed by oxidation afford function- alized furans and benzofurans, respectively. Synthetic potential of the obtained products was demonstrated by synthesizing hetaryl- substituted heterocycles, which may find an application in materials chemistry. Keywords furan benzofuran heterocycle methodology building block Received: 17.05.22 Revised: 23.06.22 Accepted: 25.06.22 Available online: 12.07.22 1. Introduction Organic molecules have an opportunity for replacing the traditional inorganic compounds in functional materials due to their low cost, flexibility in designing physical and chemical properties, and simplicity of the manufacturing processes [1, 2]. The possibility for the organic compounds to act as active components of solar cells [3], optoelec- tronic devices [4], sensors [5, 6] and other materials [7, 8] has been the focus of extensive research. The functional properties of heterocyclic architectures, which have certain advantages over carbocyclic counter- parts [9], have been intensively studied [10, 11]. Histori- cally, thiophene derivatives were among the first to be used as substrates to obtain functional materials for or- ganic electronics [12]. In turn, furans, being oxygen- containing analogs with better solubility as well as with other suitable physicochemical features [13] could com- pete with thiophenes; however, their use as integral parts of functional materials started to be investigated just re- cently. Thus, the potential applications of furans and ben- zofurans in photovoltaics [14–16] and optoelectronics [17, 18] are being evaluated currently with a specific focus on hetaryl-substituted systems (Figure 1). To date, there are few general synthetic strategies to- ward furyl- and benzofuryl-containing heterocycles. Usual- ly, benzofurans are accessed via transition metal-catalyzed inter- or intramolecular cyclizations of phenols or their O- protected derivatives with alkenes and alkynes [19]. Suzuki- Miyaura cross-coupling is used to obtain target heterocyclic motifs possessing both benzofuran [20] and furan [21, 22] moieties. The conjugate addition/cyclization has also been successfully utilized for the synthesis of substituted furan- indol conjugates [23]. Heterogeneous catalysis with Cu@imine/Fe3O4 nanoparticles [24], graphene oxide with cascade addition/cyclization [25] was applied to obtain complex heterocyclic molecules with furyl substituents. Acid-catalyzed domino reaction of accessible alkylfu- rans [26] with ambiphilic compounds, comprehensively explored by Butin et al., serves as a convenient tool for constructing functionalized heterocyclic compounds [27]. The Butin reaction yields a wide range of heterocycles that possess alkanone fragments, including furans and benzo- furans. In the present work, we propose a way for the uti- lization of the Butin reaction products as building blocks for construction hetaryl-substituted furans [28] and ben- zofurans [29] as potential functional molecules. The syn- thetic design relies on the possibility for the oxidation of the alkanone side chain followed by chemical engagement of the formed α,β-unsaturated ketone fragment into chem- ical transformations to obtain novel heterocyclic systems [30, 31, 32] (Scheme 1). http://chimicatechnoacta.ru/ https://doi.org/10.15826/chimtech.2022.9.4.03 https://orcid.org/0000-0001-5066-4903 https://orcid.org/0000-0003-0952-7215 https://orcid.org/0000-0003-3434-5712 https://orcid.org/0000-0001-8889-9580 mailto:xx@yy.zz http://creativecommons.org/licenses/by/4.0/ https://crossmark.crossref.org/dialog/?doi=https://doi.org/10.15826/chimtech.2022.9.4.03&domain=pdf&date_stamp=2022-7-12 Chimica Techno Acta 2022, vol. 9(4), No. 20229403 ARTICLE 2 of 6 Figure 1 Furan-based molecules for material chemistry. Scheme 1 Known synthetic strategies toward hetaryl-substituted furans and benzofurans and our protocol. 2. Experimental 1H and 13C NMR spectra were recorded with a «Bruker Avance III HD 400» (400 MHz for 1H and 101 MHz for 13C NMR) spectrometer at room temperature; the chemical shifts (δ) were measured in ppm with respect to the sol- vent (CDCl3, 1Н: δ = 7.26 ppm, 13C: δ = 77.16 ppm). Cou- pling constants (J) are given in Hertz. Splitting patterns of apparent multiplets associated with an averaged coupling constants were designated as s (singlet), d (doublet), t (triplet), m (multiplet), and br (broadened). GC/MS analy- sis was performed on an «Agilent 7890В» interfaced to an «Agilent 5977А» mass selective detector. Melting points were determined with a «Stuart SMP 30». Column chro- matography was performed on silica gel Macherey Nagel (40–63 μm). Reaction progress was monitored by GC/MS analysis and thin layer chromatography (TLC) on alumi- num backed plates with Merck Kiesel 60 F254 silica gel. The TLC plates were visualized either by UV radiation at a wavelength of 254 nm. All the reactions were carried out using dried and freshly distilled solvent. 2.1. General method for synthesis of furans A 5 mL microreaction vial equipped with a stirring bar and a Teflon cap was charged with unsaturated ketone 1 (1 mmol), 2-methylfuran (2) (1.5 mmol, 123 mg, 1.5 equiv), AcOH (5 mL), and 48% aq. HBr (8.4 mg, 5.6 μL, 5% mol). The vial was closed and placed into an aluminum heating block preheated to 80 °C, and the mixture was stirred for 12 h (TLC control). Upon completion, the reaction mixture was filtered through a thin layer of silica gel. The solvent Chimica Techno Acta 2022, vol. 9(4), No. 20229403 ARTICLE 3 of 6 was evaporated, and the residue was dissolved in di- chloromethane (2 ml) and DDQ (1.2 mmol, 272 mg, 1.2 equiv.) was added. The mixture was stirred at room tem- perature until full consumption of the starting material (TLC control). Upon completion, the reaction mixture was subjected to column chromatography on silica gel (eluent: dichloromethane/petroleum ether, 1:1). 2.1.1. (E)-4-(3,5-diphenylfuran-2-yl)but-3-en-2-one (3a) Yellow needles. Yield 265 mg (92%); mp = 112–113 °C (ethanol). Rf = 0.45 (petroleum ether/ethyl acetate, 3:1). 1H NMR (400 MHz, CDCl3): δ 7.82–7.75 (m, 2H), 7.51–7.32 (m, 9H), 6.90 (s, 1H), 6.84 (d, J = 15.6 Hz, 1H), 2.34 (s, 3H) ppm. 13C NMR (101 MHz, CDCl3): δ 197.6, 155.7, 146.1, 134.3, 132.5, 129.7, 129.1 (2C), 129.0 (2C), 128.9, 128.5 (2C), 128.3, 128.1, 124.6 (2C), 124.3, 108.8, 28.1 ppm. GC- LRMS (EI, m/z): 288 (M+, 100%), 273 ([M–CH3]+), 245 ([M–CH3CO]+). 2.1.2. (E)-4-(5-(4-methoxyphenyl)-3-phenylfuran-2-yl)but- 3-en-2-one (3b) Orange solid. Yield 264 mg (83%); mp = 142–143 °C (etha- nol). Rf = 0.40 (petroleum ether/ethyl acetate, 3:1). 1H NMR (400 MHz, CDCl3): δ 7.73–7.68 (m, 2H), 7.50–7.37 (m, 6H), 6.98–6.94 (m, 2H), 6.79 (d, J = 15.8 Hz, 1H), 6.76 (s, 1H), 3.85 (s, 3H), 2.33 (s, 3H) ppm. 13C NMR (101 MHz, CDCl3): δ 197.7, 160.4, 155.9, 145.4, 134.6, 132.6, 129.1 (2C), 128.5 (2C), 128.3, 128.3, 126.2 (2C), 123.7, 122.6, 114.5 (2C), 107.4, 55.5, 28.1 ppm. GC-LRMS (EI, m/z): 318 (M+, 100%), 303 ([M–CH3]+), 275 ([M–CH3CO]+). 2.1.3. (E)-4-(3,5-bis(4-methoxyphenyl)furan-2-yl)but-3-en- 2-one (3c) Brown solid. Yield 261 mg (75%); mp = 137–139 °C (etha- nol). Rf = 0.28 (petroleum ether/ethyl acetate, 4:1). 1H NMR (400 MHz, CDCl3) δ 7.73–7.68 (m, 2H), 7.44 (d, J = 15.6 Hz, 1H), 7.41–7.37 (m, 2H), 7.02–6.93 (m, 4H), 6.77 (d, J = 15.6 Hz, 1H), 6.73 (s, 1H), 3.86 (s, 3H), 3.858 (s, 3H), 2.32 (s, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ 197.6, 160.4, 159.9, 155.9, 145.2, 134.5, 129.8 (2C), 128.4, 126.27 (2C), 125.1, 123.3, 122.8, 114.7 (2C), 114.6 (2C), 107.5, 55.5 (2C), 28.1 ppm. GC-LRMS (EI, m/z): 348 (M+, 100%), 333 ([M–CH3]+), 305 ([M–CH3CO]+). 2.2. General method for synthesis of benzofurans To a solution of salicyl alcohol 4 (0.5 mmol) in dichloro- ethane (2 mL) was added 2-methylfuran (2) (0.75 mmol, 61.5 mg, 1.5 equiv.) and trifluoromethanesulfonic acid (0.05 mmol, 7.5 mg, 0.1 equiv.). The resulting mixture was stirred at 80 °C until full consumption of the starting ma- terial (TLC control, ca. 1 h). Upon completion, the reaction mixture was filtered through a thin layer of silica gel, and DDQ (0.6 mmol, 136 mg, 1.2 equiv.) was added. The mix- ture was stirred at room temperature until full consump- tion of the starting material (TLC control). Upon comple- tion, the reaction mixture was subjected to column chro- matography on silica gel (eluent: ethyl acetate/petroleum ether, 1:20). 2.2.1. (E)-4-(3-phenylbenzofuran-2-yl)but-3-en-2-one (5a) Orange solid. Yield 127 mg (97%); mp = 102–104 °C (etha- nol). Rf = 0.56 (petroleum ether/ethyl acetate, 1:1). 1H NMR (400 MHz, CDCl3) δ 7.67–7.63 (m, 1H), 7.56–7.40 (m, 8H), 7.31–7.26 (m, 1H), 6.98 (d, J = 15.7 Hz, 1H), 2.35 (s, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ 197.6, 155.2, 148.5, 131.3, 129.7 (2C), 129.3 (2C), 128.6, 128.6, 128.5, 127.3, 127.2, 126.9, 123.7, 121.1, 111.7, 28.6 ppm. GC-LRMS (EI, m/z): 262 (M+), 247 ([M–CH3]+), 219 ([M–CH3CO]+, 100%) [33]. 2.2.2. (E)-4-(4,7-dimethoxy-3-phenylbenzofuran-2-yl)but-3- en-2-one (5b) Yellow solid. Yield 135 mg (84%); mp = 166–167 °C (etha- nol). Rf = 0.49 (petroleum ether/ethyl acetate, 1:1). 1H NMR (400 MHz, CDCl3) δ 7.42–7.33 (m, 5H), 7.26 (d, J = 15.7 Hz, 1H), 6.91 (d, J = 15.7 Hz, 1H), 6.76 (d, J = 8.6 Hz, 1H), 6.47 (d, J = 8.6 Hz, 1H), 3.94 (s, 3H), 3.60 (s, 3H), 2.22 (s, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ 197.7, 149.3, 148.4, 145.6, 140.2, 131.4, 130.9 (2C), 128.4, 128.2, 127.9 (2C), 127.5, 126.7, 119.9, 110.0, 104.1, 57.1, 56.0, 28.7 ppm. GC-LRMS (EI, m/z): 322 (M+, 100%), 307 ([M–CH3]+), 279 ([M–CH3CO]+). 2.2.3. (E)-4-(5-methoxy-7-methyl-3-phenylbenzofuran-2- yl)but-3-en-2-one (5c) Brown solid. Yield 133 mg (87%); mp = 135–136 °C (etha- nol). Rf = 0.55 (petroleum ether/ethyl acetate, 1:1). 1H NMR (400 MHz, CDCl3) δ 7.57–7.44 (m, 6H), 6.96 (d, J = 15.7 Hz, 1H), 6.88–6.85 (m, 2H), 3.80 (s, 3H), 2.55 (s, 3H), 2.35 (s, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ 197.7, 156.8, 149.4, 148.9, 131.7, 129.6 (2C), 129.3 (2C), 128.8, 128.5, 128.4, 127.4, 126.8, 122.9, 117.6, 100.2, 56.1, 28.3, 15.2 ppm. GC-LRMS (EI, m/z): 306 (M+), 291 ([M–CH3]+), 263 ([M–CH3CO]+, 100%). 2.3. General method for synthesis of pyrroles To a solution of furan 3a or benzofuran 5a (0.4 mmol) in dioxane (3 mL) was added TosMIC (0.8 mmol, 156 mg, 2 equiv.) and Cs2CO3 (0.8 mmol, 260 mg, 2 equiv.). The resulting suspension was stirred at 60 °C until full con- sumption of the starting material (TLC control, ca. 24 h). Upon completion, the reaction mixture was poured into water (200 mL) and extracted with ethyl acetate (3×20 mL). Combined organic phase was dried over anhy- drous Na2SO4, filtered and concentrated under reduced pressure. Crude concentrated extract was subjected to column chromatography on silica gel (eluent: ethyl ace- tate/petroleum ether, graduate elution from 1:5 to 1:2). 2.3.1. 1-(4-(3,5-diphenylfuran-2-yl)-1H-pyrrol-3-yl)ethan-1- one (6) Colorless oil. Yield 116 mg (89%). Rf = 0.41 (petroleum ether/ethyl acetate, 1:1). 1H NMR (400 MHz, CDCl3) δ 9.57 (br. s, 1H), 7.77–7.70 (m, 2H), 7.45–7.36 (m, 5H), 7.31–7.25 (m, 3H), 7.24–7.19 (m, 1H), 6.96 (s, 1H), 6.79 (t, J = 2.3 Hz, 1H), 2.23 (s, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ 194.7, 153.0, 143.5, 133.9, 130.8, 128.8 (2C), Chimica Techno Acta 2022, vol. 9(4), No. 20229403 ARTICLE 4 of 6 128.5 (2C), 127.5, 127.3 (2C), 126.7, 125.3, 125.3, 124.9, 123.8 (2C), 121.8, 114.0, 106.8, 28.1 ppm. GC-LRMS (EI, m/z): 327 (M+, 100%), 312 ([M–CH3]+), 284 ([M– CH3CO]+). 2.3.2. 1-(4-(3-phenylbenzofuran-2-yl)-1H-pyrrol-3-yl)ethan- 1-one (7) Colorless oil. Yield 114 mg (95%). Rf = 0.33 (petroleum ether/ethyl acetate, 1:1). 1H NMR (400 MHz, CDCl3) δ 9.42 (br. s, 1H), 7.56–7.50 (m, 1H), 7.38–7.33 (m, 1H), 7.33–7.27 (m, 2H), 7.25–7.09 (m, 6H), 6.58–6.51 (m, 1H), 2.10 (s, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ 193.9, 154.7, 146.9, 133.1, 129.2 (2C), 128.9, 128.7 (2C), 127.1, 125.8, 124.6, 124.5, 122.9, 122.0, 120.1, 119.0, 113.7, 111.4, 28.3 ppm. GC-LRMS (EI, m/z): 301 (M+, 100%), 286 ([M– CH3]+), 258 ([M–CH3CO]+). 3. Results and discussion We began our research with evaluating the possibility of synthesizing the target α,β-unsaturated carbonyl com- pounds with furyl substituent at β-position. To this end, we utilized a recently reported acid-catalyzed domino re- action of 2-methylfuran (2) with unsaturated ketones 1 that led to the formation of furylalkanones A (Scheme 2). We screened various oxidants in order to obtain respective unsaturated products 3 from alkanones A [34–36] and found that DDQ in the amount of 1.2 equiv. effectively in- duced the desired transformation affording compounds 3 with high yields. The oxidation step could be coupled with the acid-catalyzed domino reaction with the only require- ment to change the solvent after passing the initial reac- tion mixture through a pad of silica gel. The developed method was evaluated by synthesizing three examples of the target molecular architecture. In order to obtain the target benzofuryl-containing un- saturated ketones 5, we employed another acid-catalyzed domino reaction, namely, a reaction of salicyl alcohols 4 with 2-methylfuran (2) [29] (Scheme 3). The oxidative conditions found for the synthesis of compounds 3 from alkanone intermediates appeared to be suitable for obtain- ing the benzofuran counterparts 5. The oxidation step was also integrated into the process without the need to switch the solvent, and the resulting products 5a-c were obtained with high yields. The presence of a highly reactive α,β-unsaturated ke- tone fragment in the structure of the synthesized com- pounds opens prospect for applying the products 3 and 5 as building blocks for obtaining the furyl- and benzofuryl- containing heterocycles. To demonstrate this possibility, we performed the reaction of the compounds 3a and 5a with TosMIC upon activation with a base [37–40]. The reaction afforded respective pyrroles 6 and 7 with high yields (Scheme 4). The structure of the compounds 6 and 7 represents a general furyl/benzofuryl-substituted hetero- cyclic motif. Importantly, well-explored chemical behav- iour of the acetyl group and free pyrrolic nitrogen pos- sessed by the final compounds could be utilized for further structural modifications. Scheme 4 Synthesis of pyrroles 6 and 7. Scheme 2 Synthesis of furans 3. Scheme 3 Synthesis of benzofurans 5. Chimica Techno Acta 2022, vol. 9(4), No. 20229403 ARTICLE 5 of 6 4. Conclusions We developed a protocol for the synthesis of functionalized furans and benzofurans starting from easily available pre- cursors. The obtained products could serve as building blocks for designing potential furan- and benzofuran-based heterocyclic functional molecules for organic electronics. Supplementary materials No supplementary materials are available. Funding The research was supported by the Perm Research and Education Centre for Rational Use Subsoil, 2022. Acknowledgments None. Author contributions Conceptualization: D.A.M. Data curation: Y.A.V. Formal Analysis: D.A.M., Y.A.V. Funding acquisition: Y.A.V. Investigation: D.A.E., D.K.V. Methodology: D.A.E., D.K.V. Project administration: D.A.M. Resources: D.K.V., Y.A.V. Software: D.A.M., Y.A.V. Supervision: D.A.M. Validation: D.A.M., Y.A.V. Visualization: Y.A.V., D.A.M Writing – original draft: Y.A.V., D.K.V., D.A.E., D.A.M. Writing – review & editing: Y.A.V., D.A.M. Conflict of interest The authors declare no conflict of interest. Additional information Author IDs: Diana A. Eshmemet’eva, Scopus ID 57223841093; Danil K. Vshivkov, Scopus ID 57248107200; Danil A. Myasnikov, Scopus ID 57487382800. Website: Perm State University, http://en.psu.ru/. References 1. Kumar B, Kaushik BK, Negi YS. Organic thin film transistors: structures, models, materials, fabrication, and applications. a review. Polym Rev. 2014;54(1):33–111. doi:10.1080/15583724.2013.848455 2. Tsang MP, Sonnemann GW, Bassani DM. Life-cycle assessment of cradle-to-grave opportunities and environmental impacts of organic photovoltaic solar panels compared to conventional technologies. Sol Energy Mater Sol Cells. 2016;156:37–48. doi:10.1016/j.solmat.2016.04.024 3. Cao W, Jiangeng X. Recent progress in organic photovoltaics: device architecture and optical design. 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