Synthesis 2013; 45(6): 817-829
DOI: 10.1055/s-0032-1318119
paper
© Georg Thieme Verlag Stuttgart · New York

Gold and Palladium Combined for the Sonogashira Coupling of Aryl and Heteroaryl Halides

Biswajit Panda
Department of Chemistry, Indian Institute of Technology, Kharagpur 721302, India   Fax: +91(3222)282251   Email: tksr@chem.iitkgp.ernet.in
,
Tarun K. Sarkar*
Department of Chemistry, Indian Institute of Technology, Kharagpur 721302, India   Fax: +91(3222)282251   Email: tksr@chem.iitkgp.ernet.in
› Author Affiliations
Further Information

Publication History

Received: 05 December 2012

Accepted after revision: 07 January 2013

Publication Date:
15 February 2013 (online)


Abstract

A highly efficient gold and palladium combined methodology for the Sonogashira coupling of a wide array of electronically and structurally diverse aryl and heteroaryl halides is described. The orthogonal reactivity of the two metals shows high selectivity and extreme functional group tolerance in Sonogashira coupling. A brief mechanistic study reveals that the gold acetylide intermediate enters into the palladium catalytic cycle at the transmetalation step.

Supporting Information

 
  • References

  • 1 Sonogashira K, Tohda Y, Hagihara N. Tetrahedron Lett. 1975; 16: 4467
    • 2a Applied Homogeneous Catalysis with Organometallic Compounds . Cornils B, Herrmann WA. Wiley-VCH; Weinheim: 1996
    • 2b Handbook of Organopalladium Chemistry for Organic Synthesis. Negishi E, de Meijere A. Wiley; New York: 2002
    • 2c Cross-Coupling Reactions . Miyaura N. Springer; Berlin: 2000
    • 2d Metal-Catalyzed Cross-Coupling Reactions . 2nd ed. Diederich F, de Meijere A. Wiley-VCH; Weinheim: 2004
    • 2e Transition Metals for Organic Synthesis; Building Blocks and Fine Chemicals. 2nd ed. Beller M, Bolm C. Wiley-VCH; Weinheim: 2004
    • 3a Sonogashira K. J. Organomet. Chem. 2002; 653: 46
    • 3b Sonogashira K In Metal-Catalyzed Cross-Coupling Reactions . Vol. 1. Diederich F, de Meijere A. Wiley-VCH; Weinheim: 2004: 319
    • 4a Doucet H, Hierso JC. Angew. Chem. Int. Ed. 2007; 46: 834
    • 4b Chinchilla R, Najera C. Chem. Rev. 2007; 107: 874
    • 4c Plenio H. Angew. Chem. Int. Ed. 2008; 47: 6954
    • 5a Kotora M, Takahashi T In Handbook of Organopalladium Chemistry for Organic Synthesis . Negishi E, de Meijere A. Wiley; New York: 2002: 973
    • 5b Siemsen P, Livingston RC, Diederich F. Angew. Chem. Int. Ed. 2000; 39: 2632
  • 6 Mori A, Kawashima J, Shimada T, Suguro M, Hirabayashi K, Nishihara Y. Org. Lett. 2000; 2: 2935
    • 7a Fukuyama T, Shinmen M, Nishitani S, Sato M, Ryu I. Org. Lett. 2002; 4: 1691
    • 7b Alonso DA, Najera C, Pachecho MC. Tetrahedron Lett. 2002; 43: 9365
    • 7c Mery D, Heuze K, Astruc D. Chem. Commun. 2003; 1934
    • 7d Soheili A, Albaneze-Walker J, Murry JA, Dormer PG, Hughes DL. Org. Lett. 2003; 5: 4191
    • 7e Komaromi A, Novak Z. Chem. Commun. 2008; 4968
    • 7f Torborg C, Huang J, Schulz T, Schaffner B, Zapf A, Spannenberg A, Börner A, Beller M. Chem.–Eur. J. 2009; 15: 1329

      Salts or nanoparticles of gold also promote Sonogashira-type reactions, see:
    • 9a Gonzalez-Arellano C, Abad A, Corma A, Garcla H, Iglesias M, Sanchez F. Angew. Chem. Int. Ed. 2007; 46: 1536
    • 9b Li P, Wang L, Wang M, You F. Eur. J. Org. Chem. 2008; 5946
  • 10 Jones LA, Sanz S, Laguna M. Catal. Today 2007; 122: 403
    • 11a Shi Y, Peterson SM, Haberaecker III WW, Blum SA. J. Am. Chem. Soc. 2008; 130: 2168
    • 11b Duschek A, Kirsch SF. Angew. Chem. Int. Ed. 2008; 47: 5703
    • 11c Shi Y, Ramgren SD, Blum SA. Organometallics 2009; 28: 1275
    • 11d Panda B, Sarkar TK. Chem. Commun. 2010; 46: 3131
  • 12 A part of this work has appeared as a preliminary communication, see: Panda B, Sarkar TK. Tetrahedron Lett. 2010; 51: 301
    • 13a Hundertmark T, Littke AF, Buchwald SL, Fu GC. Org. Lett. 2000; 2: 1729
    • 13b Kollhofer A, Plenio H. Adv. Synth. Catal. 2005; 347: 1295
    • 13c der Heiden MA, Plenio H. Chem. Commun. 2007; 972
    • 14a Pinto A, Neuville L, Zhu J. Angew. Chem. Int. Ed. 2007; 46: 3291
    • 14b Gil-Molto J, Najera C. Eur. J. Org. Chem. 2005; 4073
    • 14c Alonso DA, Najera C, Pacheco M. Adv. Synth. Catal. 2003; 345: 1146
    • 14d Mio MJ, Kopel LC, Braun JB, Gadzikwa TL, Hull KL, Brisbois RG, Mrkworth CJ, Grieco PA. Org. Lett. 2002; 4: 3199
    • 15a Yoneda N, Matsuoka S, Miyaura N, Fukuhara T, Suzuki A. Bull.Chem. Soc. Jpn. 1990; 63: 2124
    • 15b Sakamoto T, Shiga F, Yasuhara A, Uchiyama D, Kondo Y, Yamanaka H. Synthesis 1992; 746
    • 15c Kundu NG, Dasgupta SK. J. Chem. Soc., Perkin Trans. 1 1993; 2657
    • 15d Radhakrishnan U, Stang PJ. Org. Lett. 2001; 3: 859
  • 16 Lecerclé D, Mothes C, Taran F. Synth. Commun. 2007; 37: 1301
  • 17 Firth AG, Fairlamb IJ. S, Darley K, Baumann CG. Tetrahedron Lett. 2006; 47: 3529
  • 18 Panda B, Bhadra J, Sarkar TK. Synlett 2011; 689
  • 19 Asao N, Takahashi K, Lee S, Kasahara T, Yamamoto Y. J. Am. Chem. Soc. 2002; 124: 12650
  • 20 Yao X, Li CJ. Org. Lett. 2006; 8: 1953
  • 21 Thathagar MB, Rothenberg G. Org. Biomol. Chem. 2006; 4: 111
  • 22 During the preparation of this manuscript, Wu et al. reported two cases of Sonogashira coupling of aryl triflate using our Pd(PPh3)2Cl2/AuCl(PPh3) catalytic system, see: Cao J, Miao M, Chen W, Wu L, Huang X. J. Org. Chem. 2011; 76: 9329
  • 23 Herrmann WA. Angew. Chem. Int. Ed. 2002; 41: 1290
  • 24 Dillinger S, Bertus P, Pale P. Org. Lett. 2001; 3: 1661
  • 25 Halbes UL, Pale P, Berger S. J. Org. Chem. 2005; 70: 9185
    • 26a Hirner JJ, Shi Y, Blum SA. Acc. Chem. Res. 2011; 44: 603
    • 26b Perez-Temprano MH, Casares JA, Espinet P. Chem.–Eur. J. 2012; 18: 1864
  • 27 This work was presented at the NOST conference on May 4th, 2009, Goa, India.
  • 28 Independent of each other, both the Hashmi group29 and our group12 showed that the transmetalation from organogold(I) compounds to palladium is a generally applicable methodology, and in this context the Hashmi group also showed that gold acetylide (both phosphine and NHC gold complexes)29 can enter into the palladium catalytic cycle. Incidentally, Echavarren et al.30 investigated the Pd–Au dual catalytic Sonogashira coupling thoroughly. They found that gold(I) cannot perform the Sonogashira coupling in the absence of a palladium source. This also supports our reported12 results, as AuCl(PPh3) was found to be totally inactive in the absence of the palladium complex PdCl2(PPh3)2. While the investigation by Echavarren et al. is interesting, they did not conduct the crucial ICP analysis of their catalyst, which would have shown that in the control experiments the other metal is not present.31
  • 29 Hashmi AS. K, Lothschutz C, Dopp R, Rudolph M, Ramamurthi TD, Rominger F. Angew. Chem. Int. Ed. 2009; 48: 8243
  • 30 Lauterbach T, Livendahl M, Rosellon A, Espinet P, Echavarren AM. Org. Lett. 2010; 12: 3006
  • 31 Hashmi AS. K, Lothschutz C, Dopp R, Ackermann M, Becker JD. B, Rudolph M, Scholz C, Rominger F. Adv. Synth. Catal. 2012; 354: 133