Synlett, Inhaltsverzeichnis Synlett 2017; 28(07): 825-830DOI: 10.1055/s-0036-1588941 letter © Georg Thieme Verlag Stuttgart · New York Ph3P/I2-Mediated Synthesis of 3-Aryl-Substituted and 3,4-Disubstituted Coumarins Wong Phakhodee* Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand eMail: wongp2577@gmail.com , Chuthamat Duangkamol Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand eMail: wongp2577@gmail.com , Dolnapa Yamano Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand eMail: wongp2577@gmail.com , Mookda Pattarawarapan Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand eMail: wongp2577@gmail.com › Institutsangaben Artikel empfehlen Abstract Artikel einzeln kaufen Alle Artikel dieser Rubrik Abstract Ph3P/I2–Et3N-mediated one-pot two-step esterification–cyclization toward 3-aryl coumarins and 3-aryl-4-methylcoumarins is reported. The reaction of a variety of aryl acetic acids containing steric or reactive group with 2-hydroxybenzaldehydes or 2′-hydroxyacetophenone proceeded smoothly at room temperature to afford the corresponding products in good to excellent yields using inexpensive and readily available reactants and reagents. Key words Key wordscarboxylic acids - chemoselectivity - phosphorous - cyclization Volltext Referenzen References and Notes 1a Peng X.-M, Damu GL. V, Zhou C.-H. Curr. Pharm. Des. 2013; 19: 3884 1b Medina FG, Marrero JG, Macias-Alonso M, Gonzalez MC, Cordova-Guerrero I, Teissier Garcia AG, Osegueda-Robles S. Nat. Prod. Rep. 2015; 32: 1472 1c Borges F, Roleira F, Milhazes N, Santana L, Uriarte E. Curr. Med. Chem. 2005; 12: 887 2 Sashidhara KV, Kumar A, Chatterjee M, Rao KB, Singh S, Verma AK, Palit G. Bioorg. Med. Chem. Lett. 2011; 21: 1937 3a Yang J, Liu G.-Y, Dai F, Cao X.-Y, Kang Y.-F, Hu L.-M, Tang J.-J, Li X.-Z, Li Y, Jin X.-L, Zhou B. Bioorg. Med. Chem. 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Chem. 2011; 76: 2277 20g Mamidi N, Manna D. J. Org. Chem. 2013; 78: 2386 20h Gopinath P, Vidyarini RS, Chandrasekaran S. J. Org. Chem. 2009; 74: 6291 21a Phakhodee W, Duangkamol C, Wangngae S, Pattarawarapan M. Tetrahedron Lett. 2016; 57: 325 21b Wangngae S, Duangkamol C, Pattarawarapan M, Phakhodee W. RSC Adv. 2015; 5: 25789 21c Duangkamol C, Wangngae S, Pattarawarapan M, Phakhodee W. Eur. J. Org. Chem. 2014; 7109 21d Phakhodee W, Duangkamol C, Pattarawarapan M. Tetrahedron Lett. 2016; 57: 2087 22 General Procedure To a solution of Ph3P (0.62 mmol) in CH2Cl2 (4 mL) was added I2 (0.62 mmol) at 0 °C. The resulting solution was sequentially added with aryl acetic acid (0.41 mmol) and hydroxybenzaldehyde (0.45 mmol) at 0 °C, followed by Et3N (2.05 mmol). After that, the solution was allowed to warm up to r.t. and stirred until the completion of reaction. The crude material was purified by column chromatography using EtOAc–hexanes as the eluent to afford pure product. 3-(4-Methoxyphenyl)-2H-chromen-2-one (Table 2, Entry 4) White solid (0.1013 g, 98% yield); mp 140–141 °C (lit.2 mp 140 °C); Rf = 0.38 (30% EtOAc–hexanes). 1H NMR (400 MHz, CDCl3): δ = 7.75 (s, 1 H), 7.68 (d, J = 8.8 Hz, 2 H), 7.53–7.48 (m, 2 H), 7.34 (d, J = 7.6 Hz, 1 H), 7.28 (t, J = 7.6 Hz, 1 H), 6.97 (d, J = 8.8 Hz, 2 H), 3.85 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 160.8, 160.2, 153.3, 138.5, 131.0, 129.9, 127.8, 127.1, 124.5, 119.9, 116.3, 113.9, 55.4. 6-Nitro-3-(2-nitrophenyl)-2H-chromen-2-one (Table 2, Entry 6) Yellow solid (0.0912 g, 71% yield); mp 217–218 °C; Rf = 0.41 (40% EtOAc–hexanes). 1H NMR (400 MHz, CDCl3 + TFA): δ = 8.55 (d, J = 2.4 Hz, 1 H), 8.47 (dd, J = 9.2, 2.4 Hz, 1 H), 8.22 (d, J = 7.6 Hz, 1 H), 7.94 (s, 1 H), 7.80 (t, J = 7.6 Hz, 1 H), 7.70 (t, J = 7.6 Hz, 1 H), 7.58 (d, J = 9.2 Hz, 1 H), 7.51 (d, J = 7.6 Hz, 1 H). 13C NMR (100 MHz, CDCl3+TFA): δ = 160.4, 156.8, 148.2, 144.8, 139.3, 134.6, 132.1, 131.2, 130.1, 129.0, 127.1, 125.5, 124.2, 119.5, 118.5. HRMS (ESI-TOF): m/z calcd for C15H9N2O6 [M + H]+: 313.0461; found. 313.0467. 6-Chloro-3-(2-nitrophenyl)-2H-chromen-2-one (Table 2, Entry 8) White solid (0.0832 g, 67% yield); mp 214–215 °C; Rf = 0.46 (30% EtOAc–hexanes). 1H NMR (400 MHz, CDCl3 + TFA): δ = 8.20 (d, J = 8.0 Hz, 1 H), 7.85 (s, 1 H), 7.77 (td, J = 8.0, 1.2 Hz, 2 H), 7.67 (td, J = 8.0, 1.2 Hz, 1 H), 7.62 (s, 1 H), 7.60 (dd, J = 8.8, 2.4 Hz, 1 H), 7.49 (dd, J = 8.0, 1.2 Hz, 1 H), 7.41 (d, J = 8.8 Hz, 1 H). 13C NMR (100 MHz, CDCl3 + TFA): δ = 162.6, 151.6, 148.2, 140.6, 134.5, 132.9, 132.2, 131.4, 130.9, 129.3, 127.7, 125.4, 118.6, 110.3. HRMS (ESI-TOF): m/z calcd for C15H9ClNO4 [M + H]+: 302.0220; found: 302.0226. 3-(4-Fluorophenyl)-4-methyl-2H-chromen-2-one (Table 2, Entry 18) White solid (0.0921 g, 88% yield); mp 183–184 °C; Rf = 0.30 (20% EtOAc–hexanes). 1H NMR (400 MHz, CDCl3): δ = 7.68 (dd, J = 8.0, 1.2 Hz, 1 H), 7.55 (td, J = 8.0, 1.2 Hz, 1 H), 7.36 (t, J = 8.8 Hz, 2 H), 7.31–7.26 (m, 2 H), 7.14 (td, J = 8.8, 2.0 Hz, 2 H), 2.32 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 163.9, 161.4, 161.0, 152.7, 148.1, 132.07, 131.99, 131.6, 130.4 (d, J = 14.4 Hz), 126.4, 125.3, 124.5, 120.5, 117.0, 115.70, 115.5, 16.7. HRMS (ESI-TOF): m/z calcd for C16H12FO2 [M + H]+: 255.0821; found: 255.0824. 3-(3,4-Dichlorophenyl)-4-methyl-2H-chromen-2-one (Table 2, Entry 19) White solid (0.0901 g, 72% yield); mp 209–210 °C; Rf = 0.31 (20% EtOAc–hexanes). 1H NMR (400 MHz, CDCl3 + TFA): δ = 7.76 (dd, J = 8.4, 1.6 Hz, 1 H), 7.64 (td, J = 8.4, 1.6 Hz, 1 H), 7.55 (d, J = 8.4 Hz, 1 H), 7.45–7.41 (m, 2 H), 7.41 (d, J = 2.0 Hz, 1 H), 7.15 (dd, J = 8.4, 2.0 Hz, 1 H), 2.39 (s, 3 H). 13C NMR (100 MHz, CDCl3 + TFA): δ = 163.2, 152.3, 151.4, 133.7, 133.2, 133.0, 132.7, 132.1, 130.9, 129.6, 125.6, 125.5, 124.6, 120.3, 117.3, 113.3, 16.9. HRMS (ESI-TOF): m/z calcd for C16H11ClO2 [M + H]+: 305.0136; found: 305.0129. 4-Methyl-3-(2-nitrophenyl)-2H-chromen-2-one (Table 2, Entry 20) White solid (0.0957 g, 83% yield); mp 167–168 °C; Rf = 0.37 (30% EtOAc–hexanes). 1H NMR (400 MHz, CDCl3): δ = 8.21 (d, J = 8.0 Hz, 1 H), 7.72 (td, J = 7.6, 1.2 Hz, 1 H), 7.67 (dd, J = 8.0, 1.6 Hz, 1 H), 7.62–7.55 (m, 2 H), 7.40–7.32 (m, 3 H), 2.27 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 159.9, 152.8, 148.8, 147.2, 133.8, 132.7, 131.9, 130.2, 129.8, 125.19, 125.17, 125.0, 124.6, 120.2, 117.2, 16.6. HRMS (ESI-TOF): m/z calcd for C16H12NO4 [M + H]+: 282.0766; found: 282.0767. 23a Shen W, Mao J, Sun J, Sun M, Zhang C. Med. Chem. Res. 2013; 22: 1630 23b Ye D, Wang L, Li H, Zhou J, Cao D. Sens. Actuators, B 2013; 181: 234 23c Wang L, Zou H, Ye D, Cao D. J. Heterocycl. Chem. 2013; 50: 551 23d Ranjith C, Paul N, Vijayan KK. Asian J.Chem. 2011; 23: 235 23e Pu W, Lin Y, Zhang J, Wang F, Wang C, Zhang G. Bioorg. Med. Chem. 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