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Synlett 2012; 23(10): 1529-1533
DOI: 10.1055/s-0031-1291042
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© Georg Thieme Verlag Stuttgart · New York

Potassium tert-Butoxide Promoted Cycloaddition Reaction for the Synthesis of 1,5-Disubstituted 1,2,3-Triazoles from Aromatic Azides and Trimethylsilyl-Protected Alkynes

Luyong Wu*
College of Chemistry and Chemical Engineering, Hainan Normal University, No.99, Longkun South Road, Haikou 571158, P. R. of China, Fax: +86(898)65889422.   Email: wuluyong@hainnu.edu.cn
,
Yuxue Chen
College of Chemistry and Chemical Engineering, Hainan Normal University, No.99, Longkun South Road, Haikou 571158, P. R. of China, Fax: +86(898)65889422.   Email: wuluyong@hainnu.edu.cn
,
Mi Tang
College of Chemistry and Chemical Engineering, Hainan Normal University, No.99, Longkun South Road, Haikou 571158, P. R. of China, Fax: +86(898)65889422.   Email: wuluyong@hainnu.edu.cn
,
Xinming Song
College of Chemistry and Chemical Engineering, Hainan Normal University, No.99, Longkun South Road, Haikou 571158, P. R. of China, Fax: +86(898)65889422.   Email: wuluyong@hainnu.edu.cn
,
Guangying Chen
College of Chemistry and Chemical Engineering, Hainan Normal University, No.99, Longkun South Road, Haikou 571158, P. R. of China, Fax: +86(898)65889422.   Email: wuluyong@hainnu.edu.cn
,
Xiaoping Song
College of Chemistry and Chemical Engineering, Hainan Normal University, No.99, Longkun South Road, Haikou 571158, P. R. of China, Fax: +86(898)65889422.   Email: wuluyong@hainnu.edu.cn
,
Qiang Lin
College of Chemistry and Chemical Engineering, Hainan Normal University, No.99, Longkun South Road, Haikou 571158, P. R. of China, Fax: +86(898)65889422.   Email: wuluyong@hainnu.edu.cn
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Further Information

Publication History

Received: 03 January 2012

Accepted after revision: 25 March 2012

Publication Date:
25 May 2012 (online)

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Abstract

The cycloaddition reaction of aromatic azides and trimethylsilyl alkynes upon treatment with desilylating reagents was investigated. In the process, the use of t-BuOK in wet DMF generated 1,5-disubstituted 1,2,3-triazoles regioselectively in moderate to good yields at ambient temperature.

Key words

alkynes - azides - cycloaddition - triazoles - desilylation

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
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  • References

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  • 11 Synthesis of 1,2,3-Triazoles; General Procedure: To a mixture of azide (1.0 mmol) and TMS-alkyne (1.0 mmol) in DMF (2.0 mL) with a trace of H2O (2 mg), was added t-BuOK (1.0 mmol). The reaction mixture was stirred under air at room temperature. After 24 hours, the reaction mixture was quenched by addition of sat. aq NH4Cl (5 mL) and the mixture was poured into EtOAc (45 mL) and washed with H2O (3 × 15 mL). The organic layer was dried over anhydrous Na2SO4 and filtered. The solvent was removed under reduced pressure and the residue was purified by flash chromatography (silica gel; EtOAc–petroleum ether)
  • 12 Analytic data of selected products: 1-(4-Methoxyphenyl)-5-phenyl-1H-1,2,3-triazole (3d): Yield: 71%; pale-yellow solid; mp 83–85 °C; IR (KBr): 3112, 2931, 1511, 763 cm–1; 1H NMR (CDCl3, 400 MHz): δ = 3.83 (s, 3 H), 6.92 (d, J = 8.8 Hz, 2 H), 7.22–7.24 (m, 2 H), 7.27 (d, J = 8.8 Hz, 2 H), 7.32–7.36 (m, 3 H), 7.85 (s, 1 H); 13C NMR (CDCl3, 100 MHz): δ = 55.4, 114.4, 126.5, 126.7, 128.4, 128.7, 129.0, 129.5, 133.0, 137.6, 160.0; HRMS (ESI): m/z [M + H]+ calcd for C15H13N3O: 252.1131; found: 252.1133. 1-Phenyl-5-p-tolyl-1H-1,2,3-triazole (3l): Yield: 79%; pale-yellow solid; mp 150–151 °C; IR (KBr): 3106, 2924, 1494, 762 cm–1; 1H NMR (CDCl3, 400 MHz): δ = 2.35 (s, 3 H), 7.10–7.15 (m, 4 H), 7.35–7.39 (m, 2 H), 7.42–7.44 (m, 3 H), 7.83 (s, 1 H); 13C NMR (CDCl3, 100 MHz): δ = 21.2, 123.7, 125.1, 128.4, 129.1, 129.2, 129.5, 133.1, 133.2, 136.7, 137.8, 139.3. HRMS (ESI): m/z [M + H]+ calcd for C15H13N3: 236.1182; found: 236.1182