2-Ethynylpyridine-Promoted Rapid Copper(I) Chloride Catalyzed Azide–Alkyne Cycloaddition Reaction in Water

Hidekatsu Hiroki; Kenichi Ogata; Shin-ichi Fukuzawa

doi:10.1055/s-0032-1318488

Synlett, Table of Contents

Synlett 2013; 24(7): 843-846
DOI: 10.1055/s-0032-1318488

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2-Ethynylpyridine-Promoted Rapid Copper(I) Chloride Catalyzed Azide–Alkyne Cycloaddition Reaction in Water

Hidekatsu Hiroki

Department of Applied Chemistry, Institute of Science and Engineering, Chuo University, 1-13-27 Kasuga Bunkyo-ku, Tokyo 112-8551, Japan Fax: +81(3)38171895 Email: orgsynth@kc.chuo-u.ac.jp

,

Kenichi Ogata

Department of Applied Chemistry, Institute of Science and Engineering, Chuo University, 1-13-27 Kasuga Bunkyo-ku, Tokyo 112-8551, Japan Fax: +81(3)38171895 Email: orgsynth@kc.chuo-u.ac.jp

,

Shin-ichi Fukuzawa*

Department of Applied Chemistry, Institute of Science and Engineering, Chuo University, 1-13-27 Kasuga Bunkyo-ku, Tokyo 112-8551, Japan Fax: +81(3)38171895 Email: orgsynth@kc.chuo-u.ac.jp

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Abstract

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Abstract

The copper(I) chloride catalyzed reaction of azides with alkynes in water at room temperature was promoted by the addition of a catalytic amount of 2-ethynylpyridine, affording the corresponding 1,4-disubstituted 1,2,3-triazoles in good yields after a specific reaction time. The catalytic system could be successfully applied to electron-rich, electron-poor, and sterically crowded substrates. A study of the additive effect of pyridine derivatives revealed that alkynyl and 2-pyridyl groups were essential for activating the copper catalyst.

Key words

cycloaddition - azides - alkynes - copper - heterocycles

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References

References and Notes

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4 We obtained the X-ray crystal structure of pyta–CuI complex (see Supporting Information).
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9 General Procedure for 2-Ethynylpyridine-Promoted Cu(I)-Catalyzed Azide–Alkyne 1,3-Dipolar Cycloaddition In a vial containing a magnetic stirrer bar was added CuCl (2.98 mg, 0.03 mmol), H₂O (3 mL), 2-ethynylpyridine (3.0 μL, 0.03 mmol) followed by an alkyne (1.0 mmol) and an azide (1.05 mmol) were loaded. The vial was closed with a screw cap, and the reaction mixture was stirred at specified temperature for the time specified in Table 3. The resulting solution was quenched with NH₃ solution, extracted with EtOAc, washed with brine, dried over MgSO₄, filtered, and finally the solvent was removed under reduced pressure. GC–MS analysis revealed the presence of the corresponding 1,2,3-triazole. The crude product was purified by PTLC or short silica gel column (hexane–EtOAc as eluent)

Supplementary Material

Supporting Information