Synlett, Table of Contents Synlett 2023; 34(01): 77-80DOI: 10.1055/s-0042-1753061 letter Synthesis of β-Arylbutenolides Mediated by BF3·OMe2 Beatriz M. Finêncio , Fernanda A. Santos , Rosangela S. Laurentiz∗ Recommend Article Abstract Buy Article All articles of this category Abstract The reaction of phenols or aryl ethers with tetronic acid mediated by BF3·OMe2 was investigated. This strategy allowed for the preparation of β-(hydroxyaryl)butenolides and β-arylbutenolides in a single step in a simpler way than previously reported synthetic methods Key words Key wordsbutenolides - aromatic electrophilic substitution - rubrolides - synthons - tetronic acid Full Text References References and Notes 1 John B, Nicolas L, Michel O, Martin T. Tetrahedron Lett. 1998; 39: 7665 2 Bracegirdle J, Keyzers AR. Curr. Pharm. Des. 2020; 26: 4351 3 Bracegirdle J, Stevenson LJ, Sharrock AV, Page MJ, Vorster JA, Owen JG, Ackerley DF, Keyzers RA. J. Nat. Prod. 2021; 84: 544 4 de Vries J, Assmann M, Janneschütz J, Krauß J, Gudzuhn M, Stanelle-Bertram S, Gabriel G, Streit WR, Schützenmeister N. Eur. J. Org. Chem. 2021; 29: 4195 5 Yang L.-H, Ou-Yang H, Yan X, Tang B.-W, Fang M.-J, Wu Z, Chen J.-W, Qiu Y.-K. Mar. Drugs 2018; 16: 428 6 Zhang H, Conte MM, Huang X-C, Khalil Z, Capon RJ. Org. Biomol. Chem. 2012; 10: 2656 7 Nam N.-H, Kim Y, You Y.-J, Hong D.-H, Kim H.-M, Ann B.-Z. Arch. Pharm. Res. 2002; 25: 590 8 Bellina F, Anselmi C, Martina F, Rossi R. Eur. J. Org. Chem. 2003; 2290 9 Kar A, Argad NP. Synthesis 2005; 2284 10 Schacht M, Boehlich GJ, de Vries J, Bertram S, Gabriel G, Zimmermann P, Heisig P, Schützenmeister N. Eur. J. Org. Chem. 2017; 1745 11 Tale NP, Shelke AV, Tiwari GB, Thorat PB, Karade NN. Helv. Chim. Acta 2012; 95: 852 12 Chavan P, Pathak AB, Pandey A, Kalkote UR. Synth. Commun. 2007; 37: 4253 13 Rossi R, Bellina F, Raugei E. Synlett 2000; 1749 14 Wu J, Zhu Q, Wang L, Fathi R, Yang Z. J. Org. Chem. 2003; 68: 670 15 Karak M, Barbosa LC. A, Maltha CR. A, Silva TM, Boukouvalas J. Tetrahedron Lett. 2017; 58: 2830 16 Kiyokawa K, Takemoto K, Yahata S, Kojima T, Minakata S. Synthesis 2017; 49: 2907 17 Pissurno AP. R, Laurentiz RS. Synth. Commun. 2017; 47: 1874 18 Santos FA, Tondato WN, Parreira RL. T, Orenha RP, Lourenço LC. L, Laurentiz RS. J. Lumin. 2020; 227: 117547 19 Mejia FB, Lafferty MM, Melvin SJ, Truax NJ, Kean MH, Pelkey ET. Synlett 2017; 28: 260 20 Typical Experimental Procedure A mixture of tetronic acid (1.0 mmol), phenol (1.0 mmol) or aryl ether, and BF3·OMe2 (2.0 equiv) in CHCl3 (3 mL) was taken in a reaction flask equipped with a small magnetic stirring bar and the reflux condenser. The mixture was irradiated in a microwave reactor at a power of 220 W. The reaction was monitored by TLC, and after the consumption of the starting materials, it was cooled to room temperature. The solvent was removed under vacuum, and the precipitated crude product was washed with a mixture of hexane-ethyl acetate (8:2). When sesamol was used as phenol, the mixture was maintained at room temperature under stirring for 24 h. The proceeding after the reaction was the same described above. 4-(2-Hydroxy-4,5-dimethoxyphenyl)furan-2(5H)-one (3a) 0.2149 g, 92%; mp 236–237 °C. 1H NMR (400 MHz, DMSO-d 6): δ = 10.3 (s, OH), 6.94 (s, 1 H), 6.46 (s, 1 H), 6.40 (s, 1 H), 5.21 (s, 2 H), 3.67 (s, 3 H), 3.64 (s, 3 H). 13C NMR (125 MHz, DMSO-d 6): δ = 174.4, 162.6, 152.8, 152.7, 142.1, 111.3, 109.5, 107.5, 100.4, 72.4, 56.3, 55.4. HRMS (ESI+): m/z [M + H]+ calcd for C12H12O5Na: 259.0581; found: 259.0572. 4-(6-Hydroxybenzo[d][1,3]dioxol-5-yl)furan-2(5H)-one (3b) 0.1885 g, 85%; mp 228–230 °C. 1H NMR (400 MHz, DMSO-d 6): δ = 10.63 (s, OH), 7.14 (s, 1 H), 6.54 (s, 1 H), 6.46 (s, 1 H), 6,03 (s, 2 H), 5.26 (s, 2 H). 13C NMR (125 MHz, DMSO-d 6): δ = 174.4, 162.5, 154.0, 150.8, 140.7, 109.8, 108.3, 106.4, 101.7, 97.6, 72.5. HRMS (ESI+): m/z [M + H]+ calcd for C11H8O5Na: 243.0268; found: 243.0263. 4-(2,4-Dihydroxyphenyl)furan-2(5H)-one (3c) 0.1825 g, 95%; mp 241–242 °C. 1H NMR (400 MHz, DMSO-d 6): δ = 10.56 (s, OH), 10.09 (s, OH), 7.34 (d, 1 H, J = 8.6 Hz), 6.40 (d, 1 H, J = 2.6 Hz), 6.37 (d, 1 H, J = 1.3 Hz), 6.33 (dd, 1 H, J = 2.2, 8.6 Hz), 5.26 (br s, 2 H). 13C NMR (125 MHz, DMSO-d 6): δ = 174.6, 162.4, 161.6, 159.0, 130.0, 109.8, 108.8, 107.8, 102.6, 72.5. HRMS (ESI+): m/z [M + H]+ calcd for C10H8O4Na: 215.0319; found: 215.0313. 4-(2,4-Dimethoxyphenyl)furan-2(5H)-one (3d) 0.2024 g 92%; mp 205–207 °C. 1H NMR (400 MHz, DMSO-d 6): δ = 7.52 (d, 1 H, J = 8.66 Hz), 6.69 (d, 1 H, J = 2.33 Hz), 6,64 (dd, 1 H, J = 8.65, 2.33 Hz), 6.50–6.46 (m, 1 H), 5.29 (d, 2 H, J = 1.55 Hz), 3.90 (s, 3 H), 3.84 (s, 3 H). 13C NMR (125 MHz, DMSO-d 6): δ = 174.3, 163.3, 161.1, 160.0, 130.0, 111.2, 111.0, 106.2, 98.6, 72.1, 55.8, 55.6. HRMS (ESI+): m/z [M + Na]+ calcd for C12H12O4Na: 243.0633; found: 243.0632. 21 Cacchi S, Fabrizi G, Goggiamani A, Sferrazza A. Synlett 2009; 1277 22 Chang C.-W, Chang H.-S, Cheng M.-J, Peng C.-F, Chen I.-S. Helv. Chim. Acta 2018; 98: 347 23 Rao KV, Sadhukhan AK, Veerender M, Ravikumar V, Mohan EV, Dhanvantri SD, Sitaramkumar M, Babu JM, Vyas K, Reddy GO. Chem. Pharm. Bull. 2000; 48: 559 24 Atzeni F, Sarzi-Puttini P. Tumor Necrosis Factor . In Brenner's Encyclopedia of Genetics, 2nd ed. . Maloy S, Hughes K. Elsevier; Amsterdam: 2013 Supplementary Material Supplementary Material Supporting Information
