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

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

Key words

sulfonamides - palladium catalysis - sulfinates - amines - aryl halides

• 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