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Synlett 2014; 25(13): 1859-1862
DOI: 10.1055/s-0034-1378327
DOI: 10.1055/s-0034-1378327
letter
Regioselective N/C-Heterocyclization of Allenylindium Bromide Across Aryl Azides: One-Pot Synthesis of 5-Methyl-1,2,3-triazoles
Weitere Informationen
Publikationsverlauf
Received: 12. März 2014
Accepted after revision: 20. Mai 2014
Publikationsdatum:
12. Juni 2014 (online)
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Abstract
An unprecedented, one-pot regioselective synthesis of 1,5-disubstituted 1,2,3-triazoles through N/C-heterocyclization of allenylindium bromide across aryl azides is described. The synthesis is carried out under mild conditions in aqueous medium and proceeds regioselectively in moderate to good yields.
Key words
heterocyclization - aryl azides - 1,2,3-triazoles - allenylindium bromide - regioselective reactionsSupporting Information
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
- Supporting Information
-
References and Notes
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- 17 Typical Procedure for the Synthesis of 1-Phenyl-5-methyl-1,2,3-triazole (6a, Table 2): In a typical procedure, a suspension of indium powder (0.344 g, 3 mmol, 100 mesh, 99.99% pure), and propargyl bromide (00.238 g, 2 mmol) in THF–H2O (1:1; 20 mL) was stirred at an ambient temperature for 3 h until the metal dissolved completely to form allenylindium bromide. Phenyl azide (0.238 g, 2 mmol) was charged into the reaction mixture at ambient conditions over a period of 2 min. After 5 min, n-butylamine (5 mol%) was charged into the reaction mixture as an additive and the reaction was allowed to stir at 50 °C for 6 h till TLC proved a significant conversion. The reaction was finally quenched with aq NH4Cl solution (10 mL) followed by dilution with another 50 mL. The organic layer was separated and the aqueous layer was extracted with CH2Cl2 (2 × 20 mL). The combined organic layers were dried (anhyd Na2SO4) and evaporated under reduced pressure to afford a crude product, which was subjected to chromatography (Alumina, mean pore diameter 60 Å, eluent: n-hexane–EtOAc gradient) to afford pure 1-phenyl-5-methyl-1,2,3-triazole as a pale yellow solid (0.244 g, 1.54 mmol, 77%); mp 61–62 °C. IR (KBr): 1234, 1494, 1549, 1593, 2922, 3138 cm–1. 1H NMR (400 MHz, CDCl3): δ = 2.37 (s, 3 H), 7.48–7.50 (m, 2 H), 7.52–7.58 (m, 3 H), 7.70 (s, 1 H). 13C NMR (400 MHz, CDCl3): δ = 10.3, 125.6, 129.6, 129.8, 130.6, 138.5, 141.2. HRMS (ESI–TOF): m/z [M + H]+ for C9H9N3: 160.0796.
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- 20 Most of the compounds (6a–m) are already known in the literature through the methods discussed in the main text along with the required references. However, full spectral details of all unknown analogues have been provided in the supporting information.