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Platinum Metals Rev., 2011, 55, (3), 212

doi:10.1595/147106711x579128

Final Analysis: Is Gold a Catalyst in Cross-Coupling Reactions in the Absence of Palladium?

    • Madeleine Livendahl
    • Institute of Chemical Research of Catalonia (ICIQ),
    • Av. Països Catalans 16, E-43007 Tarragona, Spain
    • Pablo Espinet
    • IU CINQUIMA/Química Inorgánica,
    • Facultad de Ciencias, Universidad de Valladolid, E-47071 Valladolid, Spain
    • and Antonio M. Echavarren**
    • Institute of Chemical Research of Catalonia (ICIQ),
    • Av. Països Catalans 16, E-43007 Tarragona, Spain

*Email: aechavarren@iciq.es

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In the last decade gold has emerged as a kind of “philosopher's stone” in catalysis, being able to promote a bewildering variety of transformations, including cross-coupling reactions for the formation of carbon–carbon bonds. These highly useful transformations were developed in part by the 2010 Nobel Prize awardees Richard Heck, Ei-ichi Negishi and Akira Suzuki (1) and with contributions from many other research groups. Recently, there has been some question over whether gold can catalyse these reactions which have been traditionally catalysed by palladium complexes.

In 2007, Corma's research group published a paper with the suggestive title ‘Catalysis by Gold(I) and Gold(III): A Parallelism between Homo- and Heterogeneous Catalysts for Copper-Free Sonogashira Cross-Coupling Reactions’ (2). This work stressed the similar behaviour of well-known homogeneous gold(I) complexes such as AuCl(PPh3) with that of heterogeneous gold on ceria (Au/CeO2) as catalysts for the Sonogashira coupling reaction. In addition to AuCl(PPh3), a trinuclear Au(I) complex was also claimed to be a catalyst for this reaction (Scheme I) (2–6). These homogeneous gold(I) catalysts were also reported to catalyse the Suzuki coupling of iodobenzenes with arylboronic acids (5, 6).

Scheme I.

Can a homogeneous gold(I) complex catalyse the Sonogashira coupling reaction?

Can a homogeneous gold(I) complex catalyse the Sonogashira coupling reaction?

 

Traces of Palladium

Nevertheless, from a practical perspective, it is important to note that all these reactions proceeded only under much harsher conditions (130°C in o-xylene) (2–6) than those required with palladium catalysts. Moreover, only the most reactive iodobenzenes were used as the coupling partners. Another group reported that gold(I) iodide in the presence of mono- or diphosphines as ligands acted as a catalyst for the Sonogashira coupling of iodo- and activated bromobenzenes under similar conditions (130°C in toluene) (7).

A central argument behind the development of gold catalysts for cross-coupling chemistry was that “Au(I), having the same d10 configuration as Pd(0) can catalyse reactions typically catalysed by palladium” (2–6). However, this is a rather simplistic argument, since even elements within the same group often behave very differently in catalysis.

The first step in the catalytic cycle of haloarene coupling reactions is the oxidative addition of aryl halides (ArX) to the metal catalyst. Thus, for a gold-catalysed reaction of ArX with a catalyst AuX(L) (L = ligand), a square planar Au(III) complex AuArX2(L) would be formed. There is no report for such oxidative addition. In fact, our preliminary results are pointing towards high activation barriers for these types of transformations and all our attempts to carry out the oxidative addition of a variety of iodobenzenes to AuCl(PPh3) and other Au(I) complexes in a variety of solvents led to complete recovery of the staring materials (8). This is in sharp contrast to the behaviour of PdL4 or Pd2(dba)3 + L systems, which react readily with aryl halides to give complexes PdArX(L)2. Furthermore, we failed to observe any coupling reaction between iodobenzene and phenylacetylene catalysed by gold iodide and 1,2-(diphenylphosphino)ethane. Finally, we examined a possible Sonogashira coupling proceeding via a gold(I) acetylide (Scheme II), which also met with failure.

Scheme II.

A gold(I) acetylide complex does not catalyse Sonogashira coupling

A gold(I) acetylide complex does not catalyse Sonogashira coupling

 

It has been reported that as little as 50 ppb Pd present in commercially available sodium carbonate is able to catalyse the Suzuki coupling reaction (9). Since high purity gold often contains traces of palladium, we suspected that palladium was actually responsible for the success of the Au(I)-catalysed ‘Pd-free Sonogashira reaction’. Indeed, low loadings of palladium(0) were enough to carry out the couplings in Schemes I and II (8). Therefore, we concluded that it was very unlikely that gold(I) complexes alone could act as homogeneous catalysts for cross-coupling reactions of aryl halides and closely related organic substrates (Csp2–X containing electrophiles) (8).

Gold Nanoparticles

All of the previous discussion here pertains to coupling reactions catalysed under homogeneous conditions. However, we should also consider the possibility that the reaction proceeds via heterogeneous rather than homogeneous catalysis. We have previously shown that heterogeneous and homogeneous gold catalysts activate small molecules such as alkynes and alkenes by totally different mechanisms (10). Accordingly, it is not entirely surprising to find that gold nanoparticles are efficient catalysts for the Suzuki coupling reaction (11). The reaction catalysed by gold nanoparticles prepared from hydrogen tetrachloroaurate and 2-aminothiophenol proceeded satisfactorily using chlorobenzenes as substrates, which are less reactive than iodobenzene, under conditions (80°C, 4 h) much milder that those required with Au/CeO2 (150°C, 24 h) in o-xylene (2–6).

In addition to contamination by palladium, which will depend on the particular source of gold used for the preparation of the gold complexes, is there any other way by which complexes like AuCl(PPh3) could lead to species catalytically active in cross-coupling reactions? This issue was addressed last year by Lambert's group, which demonstrated that gold nanoparticles were formed as the active catalysts by the slow decomposition of the AuCl(PPh3) complex (12–14). Thus, in the reaction between iodobenzene and phenylacetylene, long induction periods (145°C, 100 h) were required to detect the Sonogashira coupling product in low yield.

Corma's group has recently published results that further confirm the active role of gold nanoparticles in cross-coupling reactions, along with theoretical calculations that support the unlikeliness of a homogeneous Au(I)-catalysed Sonogashira coupling reaction (15), in line with our own conclusions (8).

Conclusions

Taken together, all these results show that fundamental differences exist between heterogeneous and homogeneous catalysts (10). In order to bridge the gap between these two fields, a deeper understanding of catalytic systems and their active species is required.

Thus, while gold nanoparticles may play a role in catalysing cross-coupling reactions, homogeneous gold(I) complexes are unlikely to act as catalysts for these reactions in the absence of palladium.

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References

  1.  ‘Scientific Background on the Nobel Prize in Chemistry 2010: Palladium-Catalyzed Cross Couplings in Organic Synthesis’,The Royal Swedish Academy of Sciences, Stockholm, Sweden, 6th October, 2010:http://nobelprize.org/nobel_prizes/chemistry/laureates/2010/sci.html  (Accessed on 18th May 2011) LINK http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2010/advanced-chemistryprize2010.pdf
  2.  C. González-Arellano, A. Abad, A. Corma, H. García, M. Iglesias and F. Sánchez, Angew. Chem. Int. Ed., 2007, 46, (9), 1536 LINK http://dx.doi.org/10.1002/anie.200604746
  3.  C. González-Arellano, A. Corma, M. Iglesias and F. Sánchez, Eur. J. Inorg. Chem., 2008, (7), 1107 LINK http://dx.doi.org/10.1002/ejic.200700955
  4.  A. Corma, C. González-Arellano, M. Iglesias, S. Pérez-Ferreras and F. Sánchez, Synlett, 2007, (11), 1771 LINK http://dx.doi.org/10.1055/s-2007-984500
  5.  C. González-Arellano, A. Corma, M. Iglesias and F. Sánchez, J. Catal., 2006, 238, (2), 497 LINK http://dx.doi.org/10.1016/j.jcat.2005.12.015
  6.  A. Corma, E. Gutiérrez-Puebla, M. Iglesias, A. Monge, S. Pérez-Ferreras and F. Sánchez, Adv. Synth. Catal., 2006, 348, (14), 1899 LINK http://dx.doi.org/10.1002/adsc.200606163
  7.  P. Li, L. Wang, M. Wang and F. You, Eur. J. Org. Chem., 2008, (35), 5946 LINK http://dx.doi.org/10.1002/ejoc.200800765
  8.  T. Lauterbach, M. Livendahl, A. Rosellón, P. Espinet and A. M. Echavarren, Org. Lett., 2010, 12, (13), 3006 LINK http://dx.doi.org/10.1021/ol101012n
  9.  R. K. Arvela, N. E. Leadbeater, M. S. Sangi, V. A. Williams, P. Granados and R. D. Singer, J. Org. Chem., 2005, 70, (1), 161 LINK http://dx.doi.org/10.1021/jo048531j
  10.  M. García-Mota, N. Cabello, F. Maseras, A. M. Echavarren, J. Pérez-Ramírez and N. López, ChemPhysChem, 2008, 9, (11), 1624 LINK http://dx.doi.org/10.1002/cphc.200800246
  11.  J. Han, Y. Liu and R. Guo, J. Am. Chem. Soc., 2009, 131, (6), 2060 LINK http://dx.doi.org/10.1021/ja808935n
  12.  G. Kyriakou, S. K. Beaumont, S. M. Humphrey, C. Antonetti and R. M. Lambert, ChemCatChem, 2010, 2, (11), 1444 LINK http://dx.doi.org/10.1002/cctc.201000154
  13.  V. K. Kanuru, G. Kyriakou, S. K. Beaumont, A. C. Papageorgiou, D. J. Watson and R. M. Lambert, J. Am. Chem. Soc., 2010, 132, (23), 8081 LINK http://dx.doi.org/10.1021/ja1011542
  14.  S. K. Beaumont, G. Kyriakou and R. M. Lambert, J. Am. Chem. Soc., 2010, 132, (35), 12246 LINK http://dx.doi.org/10.1021/ja1063179
  15.  A. Corma, R. Juárez, M. Boronat, F. Sánchez, M. Iglesias and H. García, Chem. Commun., 2010, 47, (5), 1446 LINK http://dx.doi.org/10.1039/C0CC04564K

The Authors

Madeleine Livendahl was born in Stockholm, Sweden, in 1983. She obtained her Master of Science in Chemistry from Stockholm University. In 2009 she joined the research group of Professor Antonio M. Echavarren at the Institute of Chemical Research of Catalonia (ICIQ) in Tarragona, Spain, with a predoctoral ICIQ fellowship. Her research interests are the discovery of new transition metal-catalysed reactions.

Pablo Espinet, born in Borja (Zaragoza, Spain) is Professor of Inorganic Chemistry in the University of Valladolid, Spain. He is Director of the research institute CINQUIMA (Center for Innovation in Chemistry and Advanced Materials). His research covers the experimental study of reaction mechanisms of palladium-catalysed reactions and the synthesis of functional metal-containing molecules.

Antonio M. Echavarren, born in Bilbao (Basque Country, Spain) is Professor of Organic Chemistry and Group Leader in the Institute of Chemical Research of Catalonia (ICIQ) in Tarragona, Spain. His research interests centre on the development of new catalytic methods based on the organometallic chemistry of transition metals as well as the synthesis of natural products and polyarenes.

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