Synthesis 2013; 45(12): 1635-1640
DOI: 10.1055/s-0033-1338468
special topic
© Georg Thieme Verlag Stuttgart · New York

Mild and Selective Organocatalytic Iodination of Activated Aromatic Compounds

Gergely Jakab
Institute of Organic Chemistry, Justus-Liebig University Giessen, Heinrich-Buff-Ring 58, 35392 Giessen, Germany   Fax: +49(641)9934309   Email: prs@uni-giessen.de
,
Abolfazl Hosseini
Institute of Organic Chemistry, Justus-Liebig University Giessen, Heinrich-Buff-Ring 58, 35392 Giessen, Germany   Fax: +49(641)9934309   Email: prs@uni-giessen.de
,
Heike Hausmann
Institute of Organic Chemistry, Justus-Liebig University Giessen, Heinrich-Buff-Ring 58, 35392 Giessen, Germany   Fax: +49(641)9934309   Email: prs@uni-giessen.de
,
Peter R. Schreiner*
Institute of Organic Chemistry, Justus-Liebig University Giessen, Heinrich-Buff-Ring 58, 35392 Giessen, Germany   Fax: +49(641)9934309   Email: prs@uni-giessen.de
› Author Affiliations
Further Information

Publication History

Received: 23 February 2013

Accepted: 17 March 2013

Publication Date:
25 April 2013 (online)

Abstract

We describe an organocatalytic iodination of activated aromatic compounds using 1,3-diiodo-5,5-dimethylhydantoin (DIH) as the iodine source with thiourea catalysts in acetonitrile. The protocol is applicable to a number of aromatic substrates with significantly different steric and electronic properties. The iodination is generally highly regioselective and provides high yields of isolated products. NMR kinetic investigations conducted in THF-d 8 indicate the role of sulfur in the thiourea motif as a nucleophile that is assisted by H-bonding in the key steps of the reaction.

Supporting Information

 
  • References

    • 2a Koehler L, Gagnon K, McQuarrie S, Wuest F. Molecules 2010; 15: 2686
    • 2b Welch MJ, Redvanly CS. Handbook of Radiopharmaceuticals: Radiochemistry and Applications 2005
    • 2c Seevers RH, Counsell RE. Chem. Rev. 1982; 82: 575
    • 3a Stavber S, Jereb M, Zupan M. Synthesis 2008; 1487
    • 3b Merkushev EB. Synthesis 1988; 923
    • 4a Mortensen MA, Guo C, Reynolds NT, Wang L, Helle MA, Keefe DK, Haney BP, Paul BJ, Bruzinski PR, Wolf MA, Malinowski NL, Yang Q. Org. Process Res. Dev. 2012; 16: 1811
    • 4b Shen H, Vollhardt KP. C. Synlett 2012; 23: 208
    • 4c Zhou C.-Y, Li J, Peddibhotla S, Romo D. Org. Lett. 2010; 12: 2104
    • 4d Bovonsombat P, Leykajarakul J, Khan C, Pla-on K, Krause MM, Khanthapura P, Ali R, Doowa N. Tetrahedron Lett. 2009; 50: 2664
    • 4e Bovonsombat P, Khanthapura P, Krause MM, Leykajarakul J. Tetrahedron Lett. 2008; 49: 7008
    • 4f Chaikovskii V, Filimonov V, Skorokhodov V, Ogorodnikov V. Russ. J. Org. Chem. 2007; 43: 1278
    • 4g Yadav JS, Reddy BV. S, Reddy PS. R, Basak AK, Narsaiah AV. Adv. Synth. Catal. 2004; 346: 77
    • 4h Pu Y.-M, Grieme T, Gupta A, Plata D, Bhatia AV, Cowart M, Ku Y.-Y. Org. Process Res. Dev. 2004; 9: 45
    • 4i Castanet A.-S, Colobert F, Broutin P.-E. Tetrahedron Lett. 2002; 43: 5047
    • 4j Carreño MC, García Ruano JL, Sanz G, Toledo MA, Urbano A. Tetrahedron Lett. 1996; 37: 4081
    • 4k Olah GA, Wang Q, Sandford G, Surya Prakash GK. J. Org. Chem. 1993; 58: 3194
    • 4l Bovonsombat P, Angara GJ, McNelis E. Synlett 1992; 131
    • 5a Kamei T, Shibaguchi H, Sako M, Toribatake K, Shimada T. Tetrahedron Lett. 2012; 53: 3894
    • 5b Chaikovskii V, Filimonov VD, Funk AA, Skorokhodov VI, Ogorodnikov VD. Russ. J. Org. Chem. 2007; 43: 1291
    • 5c Raab CE, Dean DC, Melillo DG. J. Labelled Compd. Radiopharm. 2001; 44: 815
    • 5d Orazi OO, Corral A, Bertorello HE. J. Org. Chem. 1965; 30: 1101
  • 6 Selected example: Prakash GK. S, Mathew T, Hoole D, Esteves PM, Wang Q, Rasul G, Olah GA. J. Am. Chem. Soc. 2004; 126: 15770
    • 7a Wittkopp A, Schreiner PR. Diels–Alder Reactions in Water and in Hydrogen-Bonding Environments. In The Chemistry of Dienes and Polyenes. Vol. 2. Rappoport Z. John Wiley & Sons Inc.; Chichester: 2000: 1029
    • 7b Schreiner PR, Wittkopp A. Org. Lett. 2002; 4: 217
  • 9 Curran DP, Kuo LH. J. Org. Chem. 1994; 59: 3259
  • 10 Tripathi CB, Mukherjee S. J. Org. Chem. 2012; 77: 1592
    • 11a Denmark SE, Kuester WE, Burk MT. Angew. Chem. Int. Ed. 2012; 51: 10938
    • 11b Zhou L, Chen J, Tan CK, Yeung Y.-Y. J. Am. Chem. Soc. 2011; 133: 9164
    • 11c Denmark SE, Burk MT. Proc. Natl. Acad. Sci. U.S.A. 2010; 107: 20655
    • 12a Tan CK, Le C, Yeung Y.-Y. Chem. Commun. 2012; 48: 5793
    • 12b Chen J, Zhou L, Yeung Y.-Y. Org. Biomol. Chem. 2012; 10: 3808
    • 12c Chen J, Zhou L, Tan CK, Yeung Y.-Y. J. Org. Chem. 2012; 77: 999
    • 12d Tan CK, Zhou L, Yeung Y.-Y. Org. Lett. 2011; 13: 2738
    • 12e Zhou L, Tan CK, Jiang X, Chen F, Yeung Y.-Y. J. Am. Chem. Soc. 2010; 132: 15474
  • 13 Aragoni MC, Arca M, Devillanova FA, Isaia F, Lippolis V. Cryst. Growth Des. 2012; 12: 2769
    • 14a Papayannis DK, Kosmas AM. THEOCHEM 2008; 851: 175
    • 14b Aragoni MC, Arca M, Devillanova FA, Grimaldi P, Isaia F, Lelj F, Lippolis V. Eur. J. Inorg. Chem. 2006; 2166
    • 14c Aragoni MC, Arca M, Demartin F, Devillanova FA, Garau A, Isaia F, Lippolis V, Verani G. J. Chem. Soc., Dalton Trans. 2005; 2252
    • 14d Corban GJ, Hadjikakou SK, Hadjiliadis N, Kubicki M, Tiekink ER. T, Butler IS, Drougas E, Kosmas AM. Inorg. Chem. 2005; 44: 8617
    • 14e Antoniadis C.D, Hadjikakou S.K, Hadjiliadis N, Kubicki M, Butler I.S. Eur. J. Inorg. Chem. 2004; 4324
    • 14f Antoniadis C.D, Corban G.J, Hadjikakou S.K, Hadjiliadis N, Kubicki M, Warner S, Butler IS. Eur. J. Inorg. Chem. 2003; 1635
    • 14g Daga V, Hadjikakou SK, Hadjiliadis N, Kubicki M, dos Santos JH. Z, Butler I.S. Eur. J. Inorg. Chem. 2002; 1718
    • 14h Aragoni MC, Arca M, Demartin F, Devillanova FA, Garau A, Isaia F, Lelj F, Lippolis V, Verani G. Chem. Eur. J. 2001; 7: 3122
    • 14i Boyle PD, Godfrey SM. Coord. Chem. Rev. 2001; 223: 265
    • 14j Bricklebank NJ, Skabara PE, Hibbs DB, Hursthouse MM, Abdul Malik K. J. Chem. Soc., Dalton Trans. 1999; 3007
  • 15 Rudd MD, Lindeman SV, Husebye S. Acta Chem. Scand. 1997; 51: 689
  • 16 Hernández-Torres G, Tan B, Barbas CF. Org. Lett. 2012; 14: 1858
  • 17 Galli C. J. Org. Chem. 1991; 56: 3238
  • 18 Albadi J, Abedini M, Iravani N. Chin. Chem. Lett. 2012; 23: 261
  • 19 Lippert KM, Hof K, Gerbig D, Ley D, Hausmann H, Guenther S, Schreiner PR. Eur. J. Org. Chem. 2012; 5919
  • 20 Jakab G, Tancon C, Zhang Z, Lippert KM, Schreiner PR. Org. Lett. 2012; 14: 1724
  • 21 Bordwell FG. Acc. Chem. Res. 1988; 21: 456
    • 22a Arman HD, Gieseking RL, Hanks TW, Pennington WT. Chem. Commun. 2010; 46: 1854
    • 22b Jay JI, Padgett CW, Walsh RD. B, Hanks TW, Pennington WT. Cryst. Growth Des. 2001; 1: 501
  • 23 Koestler M, Kirsch D, Hester A, Leisner A, Guenther S, Spengler B. Rapid Commun. Mass Spectrom. 2008; 22: 3275