Download PDF
Synlett 2013; 24(4): 502-506
DOI: 10.1055/s-0032-1318213
letter
© Georg Thieme Verlag Stuttgart · New York

Tin(IV) Chloride Promoted Reaction of Oxiranes with Hydrogen Peroxide

Xing Yan
a   College of Pharmaceutical Science, Soochow University, 199 Ren Ai Road, Suzhou 215123, P. R. of China   Fax: +86(512)65882089   Email: qiaochunhua@suda.edu.cn
,
Chunhua Qiao*
a   College of Pharmaceutical Science, Soochow University, 199 Ren Ai Road, Suzhou 215123, P. R. of China   Fax: +86(512)65882089   Email: qiaochunhua@suda.edu.cn
,
Zhongwu Guo
b   Department of Chemistry, Wayne State University, 5101 Cass Avenue, Detroit, Michigan 48202, USA
› Author Affiliations
Further Information

Publication History

Received: 11 December 2012

Accepted after revision: 22 January 2013

Publication Date:
06 February 2013 (online)

    Permissions and Reprints All articles of this category


Abstract

A group of substituted oxiranes were readily transformed to the corresponding β-hydroxyhydroperoxides (HHP) in good yields in ethereal SnCl4–H2O2 system in which SnCl4 acts as catalyst. Alternatively, treating oxiranes with SnCl4 first, followed by addition of ethereal H2O2 solution achieved primary gem-dihydroperoxides (DHP) in moderate yields. In the case of preparing DHP, SnCl4 first promoted the rearrangement of oxiranes to aldehydes, followed by condensation with hydrogen peroxide to provide DHP as final products.

Key words

SnCl4 - oxirane - β-hydroxyhydroperoxide - gem-dihydroperoxide

Supporting Information

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

  • References and Notes

  • 1 Kumar N, Sharma M, Rawat DS. Curr. Med. Chem. 2011; 18: 3889
    Crossref
  • 2 Amewu R, Gibbons P, Mukhtar A, Stachulski AV, Ward SA, Hall C, Rimmer K, Davies J, Vivas L, Bacsa J, Mercer AE, Nixon G, Stocks PA, O’Neill PM. Org. Biomol. Chem. 2010; 8: 2068
    Crossref
  • 3 O’Neill PM, Amewu RK, Nixon GL, Bousejra ElGarah F, Mungthin M, Chadwick J, Shone AE, Vivas L, Lander H, Barton V, Muangnoicharoen S, Bray PG, Davies J, Park BK, Wittlin S, Brun R, Preschel M, Zhang K, Ward SA. Angew. Chem. Int. Ed. 2010; 49: 5693
    Crossref
    • 4a Zizak Z, Juranic Z, Opsenica D, Solaja BA. Invest. New Drugs 2009; 27: 432
      Crossref
    • 4b Terzic N, Opsenica D, Milic D, Tinant B, Smith KS, Milhous WK, Solaja BA. J. Med. Chem. 2007; 50: 5118
      Crossref
    • 4c Opsenica D, Kyle DE, Milhous WK, Solaja BA. J. Serb. Chem. Soc. 2003; 68: 291
      Crossref
  • 5 Solaja BA, Terzic N, Pocsfalvi G, Gerena L, Tinant B, Opsenica D, Milhous WK. J. Med. Chem. 2002; 45: 3331
    Crossref
  • 6 Kirchhofer C, Vargas M, Braissant O, Dong YX, Wang XF, Vennerstrom JL, Keiser J. Acta Trop. 2011; 118: 56
    Crossref
    • 7a Singh C, Verma VP, Naikade NK, Singh AS, Hassam M, Puri SK. Bioorg. Med. Chem. Lett. 2010; 20: 4459
      Crossref
    • 7b Tang YQ, Dong YX, Wang XF, Sriraghavan K, Wood JK, Vennerstrom JL. J. Org. Chem. 2005; 70: 5103
      Crossref
    • 7c Singh C, Srivastav NC, Puri SK. Bioorg. Med. Chem. 2004; 12: 5745
      Crossref
    • 7d Yan X, Chen JL, Zhu YT, Qiao CH. Synlett 2011; 2827
      Article in Thieme Connect
    • 7e Ghorai P, Dussault PH. Org. Lett. 2009; 11: 213
      Crossref
    • 7f Terent’ev AO, Kutkin AV, Starikova ZA, Antipin MY, Ogibin YN, Nikishina GI. Synthesis 2004; 2356
      Article in Thieme Connect
    • 8a Sabbani S, La Pensee L, Bacsa J, Hedenstrom E, O’Neill PM. Tetrahedron 2009; 65: 8531
      Crossref
    • 8b Griesbeck AG, Blunk D, El-Idreesy TT, Raabe A. Angew. Chem. Int. Ed. 2007; 46: 8883
      Crossref
    • 8c Griesbeck AG, El-Idreesy TT, Lex J. Tetrahedron 2006; 62: 10615
      Crossref
    • 8d Prein M, Adam W. Angew. Chem., Int. Ed. Engl. 1996; 35: 477
      Crossref
    • 9a Li Y, Hao HD, Wu YK. Org. Lett. 2009; 11: 2691
      Crossref
    • 9b Liu Y.-H, Zhang Z.-H, Li T.-S. Synthesis 2008; 3314
      Article in Thieme Connect
    • 9c Antonelli E, D’Aloisio R, Gambaro M, Fiorani T, Venturello C. J. Org. Chem. 1998; 63: 7190
      Crossref
    • 9d Ogata Y, Sawaki Y, Shimizu H. J. Org. Chem. 1978; 43: 1760
      Crossref
    • 9e Subramanyam V, Brizuela CL, Soloway AH. J. Chem. Soc., Chem. Commun. 1976; 508
  • 10 Li Y, Hao HD, Zhang Q, Wu YK. Org. Lett. 2009; 11: 1615
    Crossref
  • 11 Ghorai P, Dussault PH. Org. Lett. 2008; 10: 4577
    Crossref
  • 12 Das B, Krishnaiah M, Veeranjaneyulu B, Ravikanth B. Tetrahedron Lett. 2007; 48: 6286
    Crossref
    • 13a Zmitek K, Zupan M, Stavber S, Iskra J. Org. Lett. 2006; 8: 2491
      Crossref
    • 13b Zmitek K, Zupan M, Stavber S, Iskra J. J. Org. Chem. 2007; 72: 6534
      Crossref
  • 14 Azarifar D, Khosravi K, Soleimanei F. Molecules 2010; 15: 1433
    Crossref
  • 15 Azarifar D, Khosravi K, Soleimanei F. Synthesis 2009; 2553
    Article in Thieme Connect
  • 16 Tada N, Cui L, Okubo H, Miura T, Itoh A. Chem. Commun. 2010; 46: 1772
    Crossref
  • 17 Tada N, Cui L, Okubo H, Miura T, Itoha A. Adv. Synth. Catal. 2010; 352: 2383
    Crossref
  • 18 Hamann HJ, Hecht M, Bunge A, Gogol M, Liebscher J. Tetrahedron Lett. 2011; 52: 107
    Crossref
    • 19a Kim HS, Nagai Y, Ono K, Begum K, Wataya Y, Hamada Y, Tsuchiya K, Masuyama A, Nojima M, McCullough KJ. J. Med. Chem. 2001; 44: 2357
      Crossref
    • 19b Kim HS, Tsuchiya K, Shibata Y, Wataya Y, Ushigoe Y, Masuyama A, Nojima M, McCullough KJ. J. Chem. Soc., Perkin Trans 1 1999; 1867
  • 20 Ishihara K In Lewis Acids in Organic Synthesis . Yamamoto H. Wiley-VCH; Weinheim: 2000: 408
    Google Scholar
  • 21 Representative Procedure for Preparing β-Hydroxyhydroperoxides (Method A, Conversion of 4a into 5a) To the ethereal H2O2 solution (1.4 mol·L–1, 2.2 mL, 3.08 mmol, 5.0 equiv) was added SnCl4–CH2Cl2 solution (1.0 mol·L–1, 0.062 mL, 62 μmol, 0.1 equiv) in an ice-bath. The mixture was stirred for 5 min. A solution of 4a (0.1 g, 0.62 mmol, 1.0 equiv) in CH2Cl2 (1.0 mL) was added slowly at this temperature. Then the mixture was warmed up to r.t. and stirred for about 1 h till the reaction was complete (TLC). The reaction mixture was diluted with Et2O (20 mL) and washed with H2O (5 mL). The organic phase was separated, the aqueous solution was extracted with EtOAc (3 × 10 mL). The combined organic phases were washed with brine (5 mL), dried over anhyd Na2SO4, and concentrated. The crude product was purified by column chromatography on silica gel (PE–EtOAc = 5:1) to afford 5a as a white solid (95 mg, 79% yield). Rf  = 0.2 (PE–EtOAc = 3:1). 1H NMR (300 MHz, CDCl3): δ = 9.42 (br s, 1 H), 7.31–7.09 (m, 5 H), 3.70 (d, J = 11.9 Hz, 1 H), 3.59 (d, J = 12.0 Hz, 1 H), 3.48 (br s, 1 H), 2.78–2.54 (m, 2 H), 2.00–1.84 (m, 1 H), 1.79–1.63 (m, 1 H), 1.21 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 142.1, 128.5 (2 C), 128.4 (2 C), 125.9, 84.67, 65.7, 35.6, 29.6, 18.3. ESI-HRMS: m/z calcd for C11H16O3Na [M + Na]+: 219.0992; found: 219.0994. Representative Procedure for Preparing Primary gem-Dihydroperoxides (Method B, Conversion of 4a into 6a) The solution of 4a (0.1 g, 0.62 mmol, 1.0 equiv) in CH2Cl2 (2 mL) was cooled to –70 °C. SnCl4–CH2Cl2 solution (1.0 mol·L–1, 0.62 mL, 0.62 mmol, 1.0 equiv) was added, and the mixture was stirred for 5 min. Then ethereal H2O2 solution (1.4 mol·L–1, 2.2 mL, 3.08 mmol, 5.0 equiv) was added quickly. The mixture was stirred for 5 min at –70 °C. The reaction vessel was warmed to r.t., and the reaction mixture was stirred for 30 min and diluted with Et2O (30 mL), washed with H2O (5 mL), sat. NaHCO3 solution (5 mL), and brine (5 mL), dried over anhyd Na2SO4, and concentrated. The crude product was purified by column chromatography on silica gel (PE–EtOAc = 10:1) to afford 6a as a colorless liquid (92 mg, 70% yield). Rf  = 0.4 (PE–EtOAc = 3:1). 1H NMR (400 MHz, CDCl3): δ = 9.38 (s, 2 H), 7.33–7.12 (m, 5 H), 5.08 (d, J = 7.2 Hz, 1 H), 2.76–2.66 (m, 1 H), 2.63–2.52 (m, 1 H), 2.05–1.86 (m, 2 H), 1.60–1.48 (m, 1 H), 1.06 (d, J = 6.7 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 141.9, 128.4 (4 C), 125.9, 114.5, 33.9, 33.2, 32.8, 14.9. ESI-HRMS: m/z calcd for C11H16O4Na [M + Na]+: 235.0941; found: 235.0943.
    • 22a Kita Y, Matsuda S, Inoguchi R, Ganesh JK, Fujioka H. Tetrahedron Lett. 2005; 46: 89
      Crossref
    • 22b Robinson MW. C, Pillinger KS, Mabbett I, Timms DA, Graham AE. Tetrahedron 2010; 66: 8377
      Crossref