Synlett 2016; 27(01): 101-105
DOI: 10.1055/s-0035-1560578
letter
© Georg Thieme Verlag Stuttgart · New York

One-Pot Sulfonamide Synthesis Exploiting the Palladium-Catalyzed Sulfination of Aryl Iodides

Emmanuel Ferrer Flegeau, Jack M. Harrison, Michael C. Willis*
  • Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, UK   Email: michael.willis@chem.ox.ac.uk
Further Information

Publication History

Received: 10 September 2015

Accepted: 25 September 2015

Publication Date:
13 October 2015 (eFirst)

Dedicated, with best wishes, to Professor Steven Ley on the occasion of his 70th birthday

Abstract

Aryl ammonium sulfinates, conveniently prepared from aryl iodides and the sulfur dioxide surrogate DABSO, under the action of a palladium(0) catalyst, are transformed in a one-pot process to a variety of functionalized sulfonamides. The sulfinate to sulfonamide transformation is achieved by simple treatment with an aqueous solution of the relevant amine and sodium hypochlorite (bleach). A broad range of amines, including anilines, and amino acid derivatives, are combined efficiently with a variety of aryl iodides, leading to sulfonamides in high yields.

Supporting Information

 
  • References


    • For example, see:
    • 1a Teall M, Oakley P, Harrison T, Shaw D, Kay E, Elliott J, Gerhard U, Castro JL, Shearman M, Ball RG, Tsou NN. Bioorg. Med. Chem. Lett. 2005; 15: 2685
    • 1b Harrak Y, Casula G, Basset J, Rosell G, Plescia S, Raffa D, Cusimano MG, Pouplana R, Pujol MD. J. Med. Chem. 2010; 53: 6560
    • 1c Smith DA, Jones RM. Curr. Opin. Drug Discovery Dev. 2008; 11: 72
  • 2 For example, see: Dale DJ, Dunn PJ, Golightly C, Hughes ML, Levett PC, Pearce AK, Searle PM, Ward G, Wood AS. Org. Process Res. Dev. 2000; 4: 17
  • 3 Furniss BS, Hannaford AJ, Smith PW. G, Tatchell AR In Vogel's Textbook of Practical Organic Chemistry . Longman Scientific and Technical; UK; 1989. 5th ed
  • 4 For example, see: Wright SW, Hallstrom KN. J. Org. Chem. 2006; 71: 1080

    • For example, see:
    • 5a Colombe JR, DeBergh JR, Buchwald SL. Org. Lett. 2015; 17: 3170

    • For a review of sulfinates in synthesis, see:
    • 5b Aziz J, Messaoudi S, Alami M, Hamze A. Org. Biolmol. Chem. 2014; 12: 9743

      For recent alternative sulfonamide syntheses, see:
    • 6a Frost CG, Hartley JP, Griffin D. Synlett 2002; 1928
    • 6b Caddick S, Wilden JD, Judd DB. J. Am. Chem. Soc. 2004; 126: 1024
    • 6c DeBergh JR, Niljianskul N, Buchwald SL. J. Am. Chem. Soc. 2013; 135: 10638
    • 6d Johnson MG, Gribble MW. Jr, Houze JB, Paras NA. Org. Lett. 2014; 16: 6248
    • 6e Young JM, Lee AG, Chandrasekaran RY, Tucker JW. J. Org. Chem. 2015; 80: 8417
  • 7 For a review of SO2 surrogates, see: Emmett EJ, Willis MC. Asian J. Org. Chem. 2015; 4: 602
    • 8a Woolven H, González-Rodríguez C, Marco I, Thompson AL, Willis MC. Org. Lett. 2011; 13: 4876
    • 8b Emmett EJ, Hayter BR, Willis MC. Angew. Chem. Int. Ed. 2013; 52: 12679
    • 8c Deeming AS, Russell CJ, Hennessy AJ, Willis MC. Org. Lett. 2014; 16: 150

    • From other laboratories:
    • 8d Waldmann C, Schober O, Haufe G, Kopka K. Org. Lett. 2013; 15: 2954
    • 8e Rocke BN, Bahnck KB, Herr M, Lavergne S, Mascitti V, Perreault C, Polivkova J, Shavnya A. Org. Lett. 2014; 16: 154
    • 8f Chun Chen C, Waser J. Org. Lett. 2015; 17: 736
  • 9 Deeming AS, Russell CJ, Willis MC. Angew. Chem. Int. Ed. 2015; 54: 1168
    • 10a Nguyen B, Emmett EJ, Willis MC. J. Am. Chem. Soc. 2010; 132: 16372
    • 10b Emmett EJ, Richards-Taylor CS, Nguyen B, Garcia-Rubia A, Hayter BR, Willis MC. Org. Biomol. Chem. 2012; 10: 4007
    • 10c Richards-Taylor CS, Blakemore DC, Willis MC. Chem. Sci. 2014; 5: 222

      Alternative catalytic syntheses of sulfonyl-derivatives from SO2 insertion:
    • 11a Ye S, Wu J. Chem. Commun. 2012; 48: 10037
    • 11b Ye S, Wu J. Chem. Commun. 2012; 48: 7753
    • 11c Li W, Li H, Langer P, Beller M, Wu X.-F. Eur. J. Org. Chem. 2014; 3101
    • 11d Wang X, Xue L, Wang Z. Org. Lett. 2014; 16: 4056

    • For a radical process that exploits DABSO to prepare N-aminosulfonamides, see:
    • 11e Zheng D, An Y, Li Z, Wu J. Angew. Chem. Int. Ed. 2014; 53: 2451
  • 12 Emmett EJ, Hayter BR, Willis MC. Angew. Chem. Int. Ed. 2014; 38: 10368
  • 13 Shavnya A, Coffey SB, Smith AC, Mascitti V. Org. Lett. 2013; 15: 6226
  • 14 For a Au(I)-catalyzed sulfinate synthesis, including examples of conversion to sulfonamides, see: Johnson MW, Bagley SW, Mankad NP, Bergman RG, Mascitti V, Toste FD. Angew. Chem. Int. Ed. 2014; 53: 4404