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Synlett 2013; 24(2): 207-210
DOI: 10.1055/s-0032-1317937
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© Georg Thieme Verlag Stuttgart · New York

Transformations of 1-(Oxiranylmethyl)-1,2,3-triazoles into 2-(Oxiranyl­methyl)-1,2,3-triazoles and Alkanenitriles

Ayumi Osawa
Department of Chemistry, Graduate School of Science, Hokkaido University, Kita-ku, Sapporo 060-0810, Japan   Fax: +81(11)7064920   Email: namba@mail.sci.hokudai.ac.jp   Email: ktanino@sci.hokudai.ac.jp
,
Akane Mera
Department of Chemistry, Graduate School of Science, Hokkaido University, Kita-ku, Sapporo 060-0810, Japan   Fax: +81(11)7064920   Email: namba@mail.sci.hokudai.ac.jp   Email: ktanino@sci.hokudai.ac.jp
,
Kosuke Namba*
Department of Chemistry, Graduate School of Science, Hokkaido University, Kita-ku, Sapporo 060-0810, Japan   Fax: +81(11)7064920   Email: namba@mail.sci.hokudai.ac.jp   Email: ktanino@sci.hokudai.ac.jp
,
Keiji Tanino*
Department of Chemistry, Graduate School of Science, Hokkaido University, Kita-ku, Sapporo 060-0810, Japan   Fax: +81(11)7064920   Email: namba@mail.sci.hokudai.ac.jp   Email: ktanino@sci.hokudai.ac.jp
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Further Information

Publication History

Received: 08 November 2012

Accepted after revision: 02 December 2012

Publication Date:
19 December 2012 (online)

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Abstract

New reactions for the transformation of 1-(oxiranylmethyl)-1,2,3-triazoles into 2-(oxiranylmethyl)-1,2,3-triazoles or alkanenitriles were established. Successive treatment of the substrate with triflic acid and t-BuOH afforded 4,6-dihydro-5-hydroxy-1,3a,6a-triazapentalene derivative. Under the influence of NaH, the bicyclic compound was converted into a 2-(oxiranylmethyl)-1,2,3-triazole or an alkanenitrile. The reaction pathway depends on the substituent pattern of the epoxide side chain.

Key words

1,2,3-triazole - 2-substituted 1,2,3-triazole - click reaction
 

  • References and Notes

    • 1a Kolb HC, Finn MG, Sharpless KB. Angew. Chem. Int. Ed. 2001; 40: 2004
      CrossrefPubMed
    • 1b Rostovtsev VV, Green LG, Fokin VV, Sharpless KB. Angew. Chem. Int. Ed. 2002; 41: 25969
    • 1c Tornøe CW, Christensen C, Meldal M. J. Org. Chem. 2002; 67: 3057
      Crossref

      For reviews, see:
    • 2a Fan WQ, Katritzky AR In Comprehensive Heterocyclic Chemistry II . Vol. 4. Katritzky AR, Rees CW, Scriven CW. V. Elsevier; Oxford: 1996: 1-126
      CrossrefGoogle Scholar
    • 2b Hein CD, Liu X.-M, Wan D. Pharm. Res. 2008; 25: 2216
      Crossref
    • 2c Struthers H, Mindt TL, Schibli R. Dalton Trans. 2010; 39: 675
      Crossref

      For recent reviews, see:
    • 3a Ling R, Yoshida M, Mariano PS. J. Org. Chem. 1996; 61: 4439
      Crossref
    • 3b Kvivopalov VP, Shkurko OP. Russ. Chem. Rev. 2005; 74: 339
      Crossref
    • 3c Bock VD, Hiemstra H, Maarseveen JH. Eur. J. Org. Chem. 2006; 1: 51
    • 3d Wu P, Fokin VV. Aldrichimica Acta 2007; 40: 7

      For recent examples, see:
    • 4a Kamijo S, Jin T, Huo Z, Yamamoto Y. J. Am. Chem. Soc. 2003; 125: 7786
      Crossref
    • 4b Kamijo S, Jin T, Huo Z, Yamamoto Y. J. Org. Chem. 2004; 69: 2386
      Crossref
    • 4c Kalisiak J, Sharpless B, Fokin VV. Org. Lett. 2008; 10: 3171
      Crossref
    • 4d Chen Y, Liu Y, Petersen JL, Shi X. Chem. Commun. 2008; 3254
    • 4e Liu Y, Yan W, Chen Y, Petersen JL, Shi X. Org. Lett. 2008; 10: 5389
      Crossref
    • 4f Wang X.-J, Zhang L, Lee H, Haddad N, Krishnamurthy D, Senanayake CH. Org. Lett. 2009; 11: 5026
      Crossref
    • 4g Wang X.-J, Sidhu K, Zhang L, Campbell S, Haddad N, Reeves DC, Krishnamurthy D, Senanayake CH. Org. Lett. 2009; 23: 5490
    • 4h Yamauchi M, Miura T, Murakami M. Heterocycles 2010; 80: 177
      Crossref
    • 4i Wang X.-J, Zhang L, Krishnamurthy D, Senanayake CH, Wipf P. Org. Lett. 2010; 12: 4632
      Crossref
    • 4j Ueda S, Su M, Buchwald SL. Angew. Chem. Int. Ed. 2011; 50: 8944
      CrossrefPubMed
    • 4k Zhang Y, Li X, Li J, Chen J, Meng X, Zhao M, Chen B. Org. Lett. 2012; 14: 26
      CrossrefPubMed
    • 4l Guru MM, Punniyamurthy T. J. Org. Chem. 2012; 77: 5063
      Crossref
  • 5 Namba K, Osawa A, Ishizaka S, Kitamura N, Tanino K. J. Am. Chem. Soc. 2011; 133: 11466
    Crossref
  • 6 Namba K, Mera A, Osawa A, Sakuda E, Kitamura N, Tanino K. Org. Lett. 2012; 14: 5554
    Crossref
  • 7 One-pot click reaction of alkyl halide, see: Kacprzak K. Synlett 2005; 943
  • 8 4-Tridecyl triazole 5a was employed for the structural analysis of the reactive intermediate cation 8a because corresponding butyl or phenyl compounds are insoluble amorphous materials in CDCl3.
  • 9 Other Brønsted and Lewis acids such as BF3·OEt2, Et2AlCl, TiCl4, Hg(OTf)2, and TFA could not activate the epoxide. However, TBSOTf and TMSOTf also gave the intermediate 8a due to in situ generated TfOH.
  • 10 We confirmed that the internal 1,2,3-triazole ring is necessary for the ring-opening reaction of oxirane leading to triflate alcohol 8. Treatment of oxirane 15 with TfOH (2.0 equiv) gave a complex mixture. Similar treatment in the presence of triazole 16 (1 equiv) also afforded the complex mixture (Scheme 4).
  • 11 Treatment of 5a with sodium hydride induced the ring-opening reaction of epoxide to give the corresponding enamino alcohol 17 in 23% yield (Scheme 5), along with recovery of starting material 5a (70%).
    • 12a The comparison of halogen atoms in the epoxide ring-closing reaction of 2,2,6,6-tetrahalogenocyclohexanols, see: Duhamel P, Leblond B, Bidois-Séry L, Poirier J.-M. J. Chem. Soc., Perkin Trans. 1 1994; 16: 2265
    • 12b Epoxide-forming reaction of 2-chloro-1-(1-chlorocyclopropyl)ethanol, see: Sudo K, Shimokawara T, Imai E, Kusano N, Kanno H, Miyake T, Mori M, Saishoji T. WO 2011070742, 2011
  • 13 Typical Procedure for the Transformation of 5a into Nitrile 10To a solution of 5a (43 mg, 0.14 mmol) in CH2Cl2 (0.7 mL) was added TfOH (25 μL, 0.28 mmol) at 0 °C. After the mixture was stirred at r.t. for 30 min, t-BuOH (1 mL) was added. The mixture was stirred for 3 h and concentrated under reduced pressure to give crude 9a. To a suspension of NaH (21 mg, 0.49 mmol) in THF (0.5 mL) was added a solution of crude 9a in THF (2.3 mL) through a cannula at 0 °C. The mixture was stirred for 3.5 h, and the reaction was quenched with sat. aq NH4Cl solution. The mixture was extracted with EtOAc (3×). The combined organic layers were washed with brine, dried over MgSO4, filtered, and concentrated under reduced pressure. The residue was purified by flash silica gel column chromatography (hexane–EtOAc, 4:1) to give nitrile 10 (22 mg, 70%) as a colorless oil. Compound 9a: 1H NMR (500 MHz, CDCl3): δ = 8.13 (s, 1 H), 5.47 (br, 1 H), 4.92 (dd, J = 14.0, 4.9 Hz, 1 H), 4.86 (dd, J = 13.2, 5.2 Hz, 1 H), 4.72 (d, J = 13.7 Hz, 1 H), 4.64 (d, J = 13.2 Hz, 1 H), 2.76 (t, J = 8.0 Hz, 2 H), 1.70–1.64 (m, 2 H), 1.36–1.26 (m, 20 H), 0.87 (t, J = 6.9 Hz, 3 H).
  • 14 The transformation of 1-(oxiranylmethyl)-1,2,3-triazoles 5 into 2-(oxiranylmethyl)-1,2,3-triazoles 6 is conducted in the same manner as the above-mentioned typical procedure.Compound 6e: white amorphous solid. 1H NMR (500 MHz, CDCl3): δ = 7.38 (s, 1 H), 4.55 (dd, J = 14.4, 6.3 Hz, 1 H), 4.48 (dd, J = 14.3, 6.3 Hz, 1 H), 3.23 (t, J = 6.0 Hz, 1 H), 2.66 (t, J = 7.7 Hz, 2 H), 1.68–1.62 (m, 2 H), 1.43 (s, 3 H), 1.36 (s, 3 H), 1.34–1.26 (m, 20 H), 0.88 (t, J = 6.9 Hz, 4 H). 13C NMR (125.8 MHz, CDCl3): δ = 149.20, 133.00, 60.86, 58.65, 53.92, 31.88, 29.64, 29.62, 29.61, 29.59, 29.51, 29.32, 29.23, 29.21, 25.44, 24.37, 22.65, 18.86, 14.08. HRMS (EI): m/z calcd for: 335.2936 [M+]; found: 335.2946.Compound 6g: 1H NMR (500 MHz, CDCl3): δ = 7.86 (s, 1 H), 7.77 (d, J = 6.9 Hz, 2 H), 7.41 (t, J = 7.4 Hz, 2 H), 7.34 (t, J = 7.4 Hz, 1 H), 4.64 (dd, J = 14.3, 5.7 Hz, 1 H), 4.54 (dd, J = 14.3, 5.7 Hz, 1 H), 3.29 (t, J = 5.7 Hz, 1 H), 1.46 (s, 3 H), 1.36 (s, 3 H).Compound 6h: 1H NMR (500 MHz, CDCl3): δ = 7.54 (s, 1 H), 4.51 (dd, J = 13.8, 5.8 Hz, 1 H), 4.48 (s, 2 H), 4.47 (dd, J = 14.3, 5.7 Hz, 1 H), 3.34 (s, 3 H), 3.18 (t, J = 5.7 Hz, 1 H), 1.37 (s, 3 H), 1.29 (s, 3 H), 1.36 (s, 3 H).Compound 6i: 1H NMR (500 MHz, CDCl3): δ = 7.37 (s, 1 H), 7.34–7.27 (m, 5 H), 4.53 (dd, J = 14.3, 5.8 Hz, 1 H), 4.52 (s, 2 H), 4.48 (dd, J = 14.3, 5.8 Hz, 1 H), 3.53 (t, J = 6.3 Hz, 2 H), 3.22 (t, J = 5.8 Hz, 1 H), 2.79 (t, J = 5.7 Hz, 2 H), 1.98 (quin, J = 6.3 Hz, 2 H), 1.43 (s, 3 H), 1.36 (s, 3 H).Compound 6j: 1H NMR (500 MHz, CDCl3): δ = 7.36 (s, 1 H), 4.47 (dd, J = 14.3, 5.8 Hz, 1 H), 4.44 (dd, J = 14.3, 5.7 Hz, 1 H), 3.52 (t, J = 6.3 Hz, 2 H), 3.16 (t, J = 5.7 Hz, 1 H), 2.79 (t, J = 6.9 Hz, 2 H), 2.08 (quin, J = 6.3 Hz, 2 H), 1.36 (s, 3 H), 1.30 (s, 3 H)