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Synlett 2017; 28(13): 1624-1629
DOI: 10.1055/s-0036-1588815
DOI: 10.1055/s-0036-1588815
letter
Palladium-Catalyzed Regioselective C-5 Arylation of 1,2,3-Triazoles with Diaryliodonium Salts
Gefördert durch: National Natural Science Foundation of China (21262028)Gefördert durch: Natural Science Foundation of Gansu Province (1208RJZA140)
Weitere Informationen
Publikationsverlauf
Received: 15. Februar 2017
Accepted after revision: 02. April 2017
Publikationsdatum:
04. Mai 2017 (online)
![](https://www.thieme-connect.de/media/synlett/201713/lookinside/thumbnails/st-2017-w0112-l_10-1055_s-0036-1588815-1.jpg)
§ These authors contributed equally to this work.
Abstract
An effective method for C-5 arylation of 1,4-disubstituted 1,2,3-triazoles and C-5 regioselective arylation of 1-substituted 1,2,3-triazoles via sp2 C–H activation with palladium as a catalyst and diaryliodonium salts as arylating reagents is described. Various electron-rich and electron-deficient substituents attached to triazoles and diaryliodonium salts were tolerable to give the desired products with good isolated yields in 24 hours under air atmosphere.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1588815.
- Supporting Information
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References and Notes
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- 15 General Procedure for Regioselective C-5 Arylation of 1,2,3-Triazoles: To a dried flask were added 1,2,3-triazoles (0.2 mmol), diaryliodonium salt (0.2 mmol), K2CO3 (2.0 equiv), Pd(OAc)2 (5 mol %), tris(o-tolyl)phosphine (10 mol%), and DMF (2 mL). Then the reaction mixture was stirred in an oil bath and heated slowly to 100 °C for 24 h. The reaction was monitored by TLC until no change was observed. The solution was cooled to r.t., and then diluted with EtOAc (10 mL). The organic phase was washed with brine (3 × 10 mL), dried over anhyd Na2SO4 and concentrated under vacuum to get the crude product. The crude product was further purified by column chromatography with hexane–EtOAc as eluent and the pure product was obtained. Diaryliodonium salts were prepared in accordance with the method previously reported by Olofsson’s group.14a 1,4-Disubstituted 1,2,3-triazoles were prepared according to our previous work.16a 1-Substituted 1,2,3-triazoles were prepared according to the previous literature.17 The analytical data of new compounds are as follows. 1-(4-Fluorobenzyl)-4-(4-fluorophenyl)-5-phenyl-1H-1,2,3-triazole (3e): white solid; yield: 46.5 mg (67%); mp 112–115 °C. 1H NMR (600 MHz, CDCl3): δ = 7.44 (dd, J = 13.8, 6.5 Hz, 3 H), 7.37 (t, J = 7.4 Hz, 2 H), 7.19 (s, 1 H), 7.06 (d, J = 7.2 Hz, 2 H), 6.90–6.97 (m, 2 H), 6.87 (q, J = 8.0 Hz, 3 H), 5.30 (s, 2 H). 13C NMR (151 MHz, CDCl3): δ = 162.4 (d, J C–F = 227.8 Hz), 143.8, 133.5, 130.9 (d, J C–F = 3.6 Hz), 129.9, 129.5, 129.4, 129.3, 128.4 (d, J C–F = 8.1 Hz), 127.6, 115.7 (d, J C–F = 21.6 Hz), 51.4. HRMS (ESI, MeOH): m/z [M + H]+ calcd for C21H16F2N3: 348.1307; found: 348.1315. IR (KBr): 3032, 2921, 2853, 1512, 1224, 843, 766, 705 cm–1. 1-(4-Fluorobenzyl)-5-phenyl-4-(4-tolyl)-1H-1,2,3-triazole (3f): white solid; yield: 52.1 mg (76%); mp 147–150 °C. 1H NMR (600 MHz, CDCl3): δ = 7.48–7.53 (m, 3 H), 7.43 (t, J = 7.5 Hz, 2 H), 7.15 (d, J = 7.3 Hz, 2 H), 7.06 (d, J = 7.8 Hz, 2 H), 6.92–6.99 (m, 4 H), 5.36 (s, 2 H), 2.30 (s, 3 H). 13C NMR (151 MHz, CDCl3): δ = 161.5 (d, J C–F = 247.1 Hz), 143.7, 137.9, 133.6, 132.3, 130.1, 129.7, 129.3, 129.2, 128.4 (d, J C–F = 8.1 Hz), 127.7, 127.5, 127.1 (d, J C–F = 3.1 Hz), 115.3 (d, J C–F = 21.5 Hz), 51.9, 21.1. HRMS (ESI, MeOH): m/z [M + H]+ calcd for C22H19FN3: 344.1558; found: 344.1564. IR (KBr): 3034, 2924, 2854, 1514, 1354, 1216, 839, 746, 696 cm–1. 1-Benzyl-5-(2-bromophenyl)-4-phenyl-1H-1,2,3-triazole (3k): pale yellow solid; yield: 59.3 mg (76%); mp 99–101 °C. 1H NMR (600 MHz, CDCl3): δ = 7.54 (d, J = 7.0 Hz, 2 H), 7.47 (d, J = 7.1 Hz, 1 H), 7.42 (t, J = 7.4 Hz, 2 H), 7.30 (d, J = 8.7 Hz, 1 H), 7.24 (s, 3 H), 7.15 (d, J = 7.2 Hz, 2 H), 7.03 (d, J = 4.6 Hz, 2 H), 6.79 (d, J = 8.7 Hz, 1 H), 5.41 (s, 2 H). 13C NMR (151 MHz, CDCl3): δ = 155.5, 144.5, 135.2, 133.9, 132.3, 130.7, 130.5, 130.1, 129.7, 129.2, 128.5, 128.2, 127.8, 127.5, 126.8, 117.4, 52.1. HRMS (ESI, MeOH): m/z [M + H]+ calcd for C21H17BrN3: 390.0601; found: 390.0609. IR (KBr): 3061, 2925, 2855, 1344, 763, 734, 695, 601 cm–1.
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