Synthesis 2016; 48(09): 1381-1388
DOI: 10.1055/s-0035-1560408
paper
© Georg Thieme Verlag Stuttgart · New York

Trihaloisocyanuric Acid/Triphenylphosphine: An Efficient System for Regioselective Conversion of Epoxides into Vicinal Halohydrins and Vicinal Dihalides under Mild Conditions

Vitor S. C. de Andrade
Departamento de Química Orgânica, Instituto de Química, Universidade Federal do Rio de Janeiro, CP 68545, Rio de Janeiro CEP 21945-970, Brazil   Email: mmattos@iq.ufrj.br
,
Marcio C. S. de Mattos*
Departamento de Química Orgânica, Instituto de Química, Universidade Federal do Rio de Janeiro, CP 68545, Rio de Janeiro CEP 21945-970, Brazil   Email: mmattos@iq.ufrj.br
› Author Affiliations
Further Information

Publication History

Received: 04 December 2015

Accepted after revision: 18 January 2016

Publication Date:
19 February 2016 (online)


Abstract

A new synthetic method has been developed for the regioselective conversion of epoxides to vicinal chloro-/bromohydrins and vicinal dihalides by reaction with the system trihaloisocyanuric acid/tri­phenylphosphine in acetonitrile under mild and neutral conditions. The reactions proceed smoothly in high yield at room temperature and at reflux, respectively, over a short time.

Supporting Information

 
  • References

  • 1 Rao AS, Paknikar SK, Kirtane JG. Tetrahedron 1983; 39: 2323
    • 3a Tsuji J, Nagashima H, Sato K. Tetrahedron Lett. 1982; 23: 3085
    • 3b Naidu KC, Babu GR, Gangaiah L, Mukkanti K, Madhusudhan G. Tetrahedron Lett. 2010; 51: 1226
    • 3c Kasai N, Suzuki T, Furukawa Y. J. Mol. Catal. B: Enzym. 1998; 4: 237
    • 3d Julia SA, Lorne R. Tetrahedron 1986; 42: 5011
    • 3e Lagos FM, Del Campo C, Llama EF, Sinisterra JV. Enzyme Microb. Technol. 2002; 30: 895
    • 4a Spargo PL. Contemp. Org. Synth. 1994; 1: 113
    • 4b Bohlmann R In Comprehensive Organic Synthesis . Vol. 6. Trost BM, Fleming I. Pergamon Press; Oxford: 1991
    • 5a Gribble GW. Chemosphere 2003; 52: 289
    • 5b Gribble GW. Prog. Org. Nat. Prod. 2010; 91: 1
  • 6 Bonini C, Righi G. Synthesis 1994; 225
  • 7 Joshi NN, Srevnik M, Brown HC. J. Am. Chem. Soc. 1988; 110: 6246
  • 8 Kotsuki H, Shimanouchi T, Ohshima R, Fujiwara S. Tetrahedron 1998; 54: 2709
  • 9 Shimizu M, Yoshida A, Fujiwara T. Synlett 1992; 204
  • 10 Loreto MA, Pellacani L, Tardella DA. Synth. Commun. 1981; 11: 287
  • 11 Palumbo G, Ferreri C, Caputo R. Tetrahedron Lett. 1983; 24: 1307
  • 12 Iranpoor N, Firouzabadi H, Azadi R, Ebrahimzadeh F. Can. J. Chem. 2006; 84: 69
  • 13 Echigo Y, Watanabe Y, Mukaiyama T. Chem. Lett. 1977; 1013
  • 14 Sonnet PE, Oliver JE. J. Org. Chem. 1976; 41: 3279
  • 15 Isaacs NS, Kirkpatrick D. Tetrahedron Lett. 1972; 3869
  • 16 Iranpoor N, Firouzabadi H, Aghapour G, Nahid A. Bull. Chem. Soc. Jpn. 2004; 77: 1885
  • 17 Yoshimitsu T, Fukumoto N, Tanaka T. J. Org. Chem. 2009; 74: 696
  • 18 Denton RM, Tang X, Przeslak A. Org. Lett. 2010; 12: 4678
  • 19 Mendonça GF, de Mattos MC. S. Curr. Org. Synth. 2013; 10: 820
  • 20 de Almeida LS, Esteves PM, de Mattos MC. S. Curr. Green Chem. 2014; 1: 94
  • 21 de Almeida LS, Esteves PM, de Mattos MC. S. Synlett 2006; 1515
  • 22 Mendonça GF, Almeida LS, de Mattos MC. S, Esteves PM, Ribeiro RS. Curr. Org. Synth. 2015; 12: 603
  • 23 Tozetti SD. F, de Almeida LS, Esteves PM, de Mattos MC. S. J. Braz. Chem. Soc. 2007; 18: 675
  • 24 de Andrade VS. C, de Mattos MC. S. J. Braz. Chem. Soc. 2014; 25: 975
    • 25a Appel R. Angew. Chem., Int. Ed. Engl. 1975; 14: 801
    • 25b de Andrade VS. C, de Mattos MC. S. Curr. Org. Synth. 2015; 12: 309
    • 26a de Luca L, Giacomelli G, Porcheddu A. Org. Lett. 2001; 3: 3041
    • 26b Crespo LT. C, de Mattos MC. S, Esteves PM. Quim. Nova 2013; 36: 320
  • 28 This ee value was calculated comparing the result we obtained, [α]D 20 +52.7 (c 1.0, CHCl3), with the previously reported for (S)-(+)-2-chloro-2-phenylethanol with 98% ee: [α]D 20 +116.1 (c 1.0, CHCl3), see: Sartillo-Piscil F, Quintero L, Santacruz-Juaréz E, de Parrodi CA. Tetrahedron Lett. 2002; 43: 15
  • 29 R-Isomer: t R = 27.46 min, S-isomer: t R = 27.59 min.
  • 30 Besse P, Renard MF, Veschambre H. Tetrahedron: Asymmetry 1994; 5: 1249
  • 31 Campbell JR, Jones JK. N, Wolfe S. Can. J. Chem. 1966; 44: 2339
  • 32 Anastas PT, Warner JC. Green Chemistry: Theory and Practice . Oxford University Press; Oxford: 2000
  • 33 Mendonça GF, Sanseverino AM, de Mattos MC. S. Synthesis 2003; 45
  • 34 Podgorsek A, Iskra J. Molecules 2010; 15: 2857
  • 35 Dewkar GK, Narina SV, Sudalai A. Org. Lett. 2003; 5: 4501
  • 36 Schmid GH, Gordon JW. Can. J. Chem. 1984; 62: 2526
  • 37 Solladié-Cavallo A, Lupattelli P, Bonini C. J. Org. Chem. 2005; 70: 1605
  • 38 Denmark SE, Barsanti PA, Wong K.-T, Savenger RA. J. Org. Chem. 1998; 63: 2428
  • 39 Caputo R, Ferreri C, Noviello S, Palumbo G. Synthesis 1986; 499
  • 40 Bellesia F, Ghelfi F, Pagnoni UM, Pinetti A. J. Chem. Res., Synop. 1989; 108
  • 41 Podgorsek A, Eissen M, Fleckenstein J, Stavber S, Zupan M, Iskra J. Green Chem. 2009; 11: 120
  • 42 Ho ML, Flynn AB, Ogilvie WW. J. Org. Chem. 2007; 72: 977
  • 43 Braddok DC, Cansell G, Hermitage SA. Synlett 2004; 461
  • 44 Zhang J, Wang J, Qiu Z, Wang Y. Tetrahedron 2011; 67: 6859
  • 45 Bailey WJ, Bello J. J. Org. Chem. 1955; 20: 525