Synthesis 2013; 45(2): 231-236
DOI: 10.1055/s-0032-1317927
paper
© Georg Thieme Verlag Stuttgart · New York

A User-Friendly Procedure for the Preparation of Secondary Alkyl Chlorides

Gérard Cahiez*
a   Chimie ParisTech, UMR CNRS 7223, 11 rue Pierre et Marie Curie, 75005 Paris, France   Email: gerard-cahiez@chimie-paristech.fr
,
Nicolas Lefèvre
a   Chimie ParisTech, UMR CNRS 7223, 11 rue Pierre et Marie Curie, 75005 Paris, France   Email: gerard-cahiez@chimie-paristech.fr
,
Maël Poizat
b   Université Paris 13, UMR CNRS 7244, 74 rue Marcel Cachin, 93017 Bobigny, France
,
Alban Moyeux
b   Université Paris 13, UMR CNRS 7244, 74 rue Marcel Cachin, 93017 Bobigny, France
› Author Affiliations
Further Information

Publication History

Received: 19 November 2012

Accepted: 26 November 2012

Publication Date:
19 December 2012 (online)


Abstract

Secondary alkyl chlorides have been efficiently prepared from secondary alkyl sulfonates under mild and user-friendly conditions. The exchange reaction was generally performed by using benzyltributylammonium chloride in acetone (reflux, 30 min). Yields are excellent from functionalized, base-sensitive and hindered secondary alkyl sulfonates.

Supporting Information

 
  • References


    • For general reviews on cross-coupling reactions with alkyl halides, see:
    • 1a Frisch AC, Beller M. Angew. Chem. Int. Ed. 2005; 44: 674
    • 1b Netherton MR, Fu GC. Adv. Synth. Catal. 2004; 346: 1525
    • 1c Càrdenas DJ. Angew. Chem. Int. Ed. 2003; 42: 384
    • 1d Westrum LJ. Fine Chemistry 2002; November/December: 10
    • 1e Luh T.-Y, Leung M.-K, Wong K.-T. Chem. Rev. 2000; 100: 3187
    • 2a Cahiez G, Habiak V, Duplais C, Moyeux A. Angew. Chem. Int. Ed. 2007; 46: 4364
    • 2b Cahiez G, Habiak V, Duplais C, Moyeux A. Org. Lett. 2007; 9: 3253
    • 3a Cahiez G, Chaboche C, Duplais C, Giulliani A, Moyeux A. Adv. Synth. Catal. 2008; 350: 1484
    • 3b Cahiez G, Chaboche C, Duplais C, Moyeux A. Org. Lett. 2009; 11: 277
    • 4a Bohlmann R. In Comprehensive Organic Synthesis . Vol. 6. Trost BM, Fleming I, Winterfeldt E. Pergamon Press; Oxford: 1991: 203
    • 4b Comprehensive Organic Transformations . Larock RC. Wiley-VCH; Weinheim: 1999: 689
  • 5 Cahiez G, Gager O, Moyeux A, Delacroix T. Adv. Synth. Catal. 2012; 354: 1519
  • 6 Winstein S, Savedoff LG, Smith S, Stevens ID. R, Gall JS. Tetrahedron Lett. 1960; 24
  • 7 Indicative prices (Acros Chemicals): Bu4NCl: 662 €/mol, BnEt3NCl: 42 €/mol, BnBu3NCl: 102 €/mol, LiCl: 10 €/mol.
    • 8a Tetrabutylammonium chloride has already been used to perform sulfonate–halide exchange reactions; however, uses for the preparation of secondary alkyl chlorides are quite rare. Moreover, the reaction is restricted to activated alkyl sulfonates like α-keto benzylic sulfonates,8a,b or to steroid8c or sugar8d derivatives. No general method has been reported for the conversion of unactivated secondary alkyl sulfonates into secondary alkyl halides with quaternary ammonium halides.
    • 8b Choi D, Stables JP, Kohn H. Bioorg. Med. Chem. 1996; 4: 2105
    • 8c Effenberger F, Kremser A, Stelzer U. Tetrahedron: Asymmetry 1996; 7: 607
    • 8d Henbest HB, Jackson WR. J. Chem. Soc. 1962; 954
    • 8e Panday N, Meyyappan M, Vasella A. Helv. Chim. Acta 2000; 83: 513

    • For some immobilized tertiary ammonium derivatives, see:
    • 8f Colonna S, Re A, Gelbard G, Cesarotti E. J. Chem. Soc., Perkin Trans. 1 1979; 2248
  • 9 When the reaction is performed with LiCl, it has been observed that the use of polar solvents favors the formation of elimination products; for instance, see ref. 5.
  • 10 Filippo JS, Silbermann J. J. Am. Chem. Soc. 1981; 103: 5588
    • 11a Madaeva OS. J. Gen. Chem. USSR (Engl. Transl.) 1955; 25: 1373
    • 11b Aneja R, Davies AP, Knaggs JA. Tetrahedron Lett. 1974; 67
    • 11c Kevill DN, Degenhardt CR, Anderson RL. J. Org. Chem. 1976; 41: 381

    • For metal salt catalyzed procedures, see:
    • 11d Lepore SD, Bhunia AK, Mondal D, Cohn PC, Lefkowitz C. J. Org. Chem. 2006; 71: 3285
    • 11e Lepore SD, Mondal D, Li SY, Bhunia AK. Angew. Chem. Int. Ed. 2008; 47: 7511
    • 11f Sun Q, Sutang P, Blake R. Org. Lett. 2009; 11: 567
    • 11g Ortega N, Brovetto M, Padron JI, Martin VS, Martin T, Feher-Voegler A. Adv. Synth. Catal. 2011; 353: 963
    • 12a Shoppee CW, Summers GH. R. J. Chem. Soc. 1952; 1790
    • 12b Shoppee CW, Holley TF, Newsoroff GP. J. Chem. Soc. 1965; 2349
    • 13a Crossland RK, Wells WE, Shiner VJ. J. Am. Chem. Soc. 1971; 93: 4217
    • 13b Robertson RE. Prog. Phys. Org. Chem. 1967; 4: 213
  • 14 Advanced Organic Chemistry; 5th ed.. Carey FA, Sundberg RJ. Springer Verlag; New York: 2007