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Synlett 2002(5): 0811-0813
DOI: 10.1055/s-2002-25343
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Mild Exchange Reaction of Xanthates with Bromine

Francis Barbier, François Pautrat, Béatrice Quiclet-Sire, Samir Z. Zard*
Laboratoire de Synthèse Organique associé au CNRS, Ecole Polytechnique, 91128 Palaiseau, France
Fax: +33(1)69333851; e-Mail: zard@poly.polytechnique.fr.;
Further Information

Publication History

Received 14 March 2002
Publication Date:
07 February 2007 (online)

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Abstract

Secondary S-alkyl-O-ethyl (or O-neopentyl) xanthates can be converted into the corresponding bromides by heating with ethyl 2-bromo-2-methylpropionate and cumyl peroxide in refluxing chlorobenzene; this transformation can be coupled to a xanthate transfer radical addition to an olefin.

Key words

bromine atom transfer - xanthates - radical reactions - lactones

    References

  • 1a Zard SZ. Angew. Chem. Int., Ed. Engl.  1997,  36:  672 ; and references cited
    Search in Google Scholar
  • 1b Quiclet-Sire B. Zard SZ. Phosphorus, Sulfur Silicon Relat. Elem.  1999,  153 
  • 1c Quiclet-Sire B. Zard SZ. Phosphorus, Sulfur Silicon Relat. Elem.  1999,  137 ; and references cited
  • 2a Kim S. Song H.-J. Choi T.-L. Yoon J.-Y. Angew. Chem. Int. Ed.  2001,  40(13):  2524 
    CrossrefSearch in Google Scholar
  • 2b Ollivier C. Renaud P. J. Am. Chem. Soc.  2000,  122(27):  6496 
    CrossrefSearch in Google Scholar
  • 2c Ollivier C. Renaud P. J. Am. Chem. Soc.  2001,  123(20):  4717 
    CrossrefSearch in Google Scholar
  • 2d Bertrand F. Le Guyader F. Liguori L. Ouvry G. Quiclet-Sire B. Seguin S. Zard SZ. C. R. Acad. Sci. Paris, Chimie 4  2001,  547 
    Crossref
  • 2e Quiclet-Sire B. Seguin S. Zard SZ. Angew. Chem. Int. Ed.  1998,  37(20):  2864 
    CrossrefSearch in Google Scholar
  • 2f Bertrand F. Quiclet-Sire B. Zard SZ. Angew. Chem. Int. Ed.  1999,  38 (13/14):  1943 
    CrossrefSearch in Google Scholar
  • 3 Liard A. Quiclet-Sire B. Zard SZ. Tetrahedron Lett.  1996,  37:  5877 
    CrossrefSearch in Google Scholar
  • 4 Castro EA. Chem. Rev.  1999,  99:  3505 
    CrossrefSearch in Google Scholar
  • 5a Boivin J. Pothier J. Ramos L. Zard SZ. Tetrahedron Lett.  1999,  40:  9239 
    CrossrefSearch in Google Scholar
  • 5b

    Typical Procedure: 1 g (4.9 mmol) of xanthate 1a and 1.8 g (9.8 mmol) of olefin 2b dissolved in 6 mL of 1,2-dichloroethane were refluxed for a few minutes under nitrogen before addition of 98 mg (0.24 mmol) of commercially available lauroyl peroxide. The reflux is maintained for another 2 h. The solvent was then removed under reduced pressure and the residue was purified by chromatography on silica gel (PE/EtOAc 9/1-7/3) to give 1.8 g of a white solid (mp 107 °C) 3b (92%). 1H NMR (CDCl3, 200 MHz, ppm): δ = 7.92-7.83 (2 H, m), 7.80-7.70 (2 H, m), 4.30 (2 H, s), 4.29 (1 H, m), 4.03 (1 H, dd, J = 7-14 Hz), 3.97 (1 H, dd, J = 7-14 Hz), 2.74-2.48 (2H, m), 2.28-1.96 (2 H, m), 1.00 (9 H, s). 13C NMR (CDCl3, 50 MHz, ppm): δ = 212.0 (C=S), 168.0 (C=O), 134.4 (CHAr), 131.9 (CqAr), 123.7 (CHAr), 118.7 (CN), 84.0 (CH2O), 48.8 (CHS), 40.4 (CH2), 32.0 (CMe3), 28.3 (CH2), 26.6 (CMe 3), 15.0 (CH2). IR (CCl4, cm-1) 2962, 2250, 1777, 1723, 1392, 1227, 1064. MS (CI): [MH]+ = 391, [MNH4]+ = 408.
    Crossref
  • 7a Murakami N. Saka M. Shimada H. Matsuda H. Yamahara J. Yoshikawa M. Chem. Pharm. Bull.  1996,  44(6):  1279 
    CrossrefSearch in Google Scholar
  • 7b Jakupovic J. Castro V. Bohlmann F. Phytochemistry  1987,  26(2):  451 
    CrossrefSearch in Google Scholar
  • 7c Herz W. Sosa VE. Phytochemistry  1986,  25(6):  1481 
    CrossrefSearch in Google Scholar
  • 7d Nagashima F. Takaoka S. Asakawa Y. Huneck S. Chem. Pharm. Bull.  1994,  42(6):  1370 
    CrossrefSearch in Google Scholar
  • 7e Götz M. Bögri A. Gray AH. Strunz GM. Tetrahedron  1968,  24:  2631 
    CrossrefSearch in Google Scholar
  • 7f Tan RX. Jia ZJ. Zhao Y. Feng SL. Phytochemistry  1992,  31(9):  3135 
    CrossrefSearch in Google Scholar
  • 7g Marco JA. Sanz-Cervera JF. Pareja JM. Sancenon F. Valles-Xirau J. Phytochemistry  1994,  37(2):  477 
    CrossrefSearch in Google Scholar
  • 8a Barton DHR. Csuhai E. Doller D. Tetrahedron  1992,  48(42):  9195 
    CrossrefSearch in Google Scholar
  • 8b Moder TI. Jensen FR. J. Am. Chem. Soc.  1975,  97(8):  2281 
    CrossrefSearch in Google Scholar
  • 8c Benedetti M. Forti L. Ghelfi F. Pagnoni UM. Ronzoni R. Tetrahedron  1997,  53(41):  14031 
    CrossrefSearch in Google Scholar
  • 8d See also: Yorimitsu H. Shinokubo H. Matsubara S. Oshima K. Omoto K. Fujimoto H. J. Org. Chem  2001,  66(23):  7776 
    CrossrefSearch in Google Scholar
  • 9 Cristol SJ. Seapy DG. J. Org. Chem.  1982,  47(1):  132 
    CrossrefSearch in Google Scholar
6

0.20 g (0.5 mmol) of xanthate 3b and 0.49 g (2.5 mmol) of ethyl 2-bromo-2-methylpropionate dissolved in 7 mL of chlorobenzene were refluxed for a few minutes under nitrogen before addition of 68 mg of commercially available cumyl peroxide. While maintaining the reflux under nitrogen, the same amount of peroxide was added every 2 h until complete disappearence of the starting xanthate. The solvent was removed under reduced pressure and the residue was purified by chromatography on silica gel (PE/EtOAc 9/1-7/3) to give after recrystallisation from ethanol 105 mg of white crystals (mp 120 °C) 5b (70%). 1H NMR (CDCl3, 400 MHz, ppm): δ = 7.90-7.85 (2 H, m), 7.78-7.40 (2 H, m), 4.38 (1 H, m) 4.14 (1 H, dd, J = 7-14 Hz), 3.99 (1 H, dd, J = 7-14 Hz), 2.72 (1 H, ddd, J = 4.5-8-17 Hz), 2.59 (1 H, td, 8-17 Hz), 2.28 (1 H, m), 2.09 (1 H, m). 13C NMR (CDCl3, 100 MHz, ppm): δ = 167.9 (C=O), 134.5 (CHAr), 131.6 (CqAr), 123.8 (CHAr), 118.4 (CN), 49.0 (CHBr), 43.8 (CH2), 31.8 (CH2), 15.9 (CH2). IR (CCl4, cm-1): 2250, 1776, 1724, 1392. MS (CI): [MNH4]+ = 324 and 326.