Theoretical Evaluation of Phosphine Effects in Cross-Coupling Reactions

  • Max García-Melchor
  • Gregori Ujaque
  • Feliu Maseras
  • Agustí Lledós
Part of the Catalysis by Metal Complexes book series (CMCO, volume 37)


Cross-coupling reactions are one of the most useful reactions in organic synthesis. Among all the transition metal complexes developed as catalysts for this reaction those based on Pd are by far the most utilized ones. The most common stoichiometry of this family of catalyst is PdL2 with L = phosphine ligands. The effects of the phosphine ligands on the reaction mechanism evaluated by means of theoretical calculations are reviewed in these lines. How the nature of the phosphine ligand affects each of the elementary processes involved in a cross-coupling reaction, namely oxidative addition, transmetalation and reductive elimination will be exposed separately. The transmetalation process has its own particular mechanistic details depending on the cross-coupling reaction; those for the Suzuki–Miyaura and Stille reactions will be described here. The dichotomy between the monophosphine and bisphosphine reaction pathways will be also discussed.


Oxidative Addition Phosphine Ligand Reductive Elimination High Energy Barrier Aryl Chloride 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



We thank the Ph.D. students and postdocs who have contributed to developing this research topic in our groups. Fruitful collaborations with experimental groups (Pablo Espinet, Gregorio Asensio, Rosana Alvarez and Angel Rodríguez de Lera) are also acknowledged. The Spanish MICINN is gratefully acknowledged for funding this research through projects CTQ2008-06866-C02-01, CTQ2008-06866-C02-02 and Consolider-Ingenio 2010 (CSD2007-00006 and CSD2006-0003).


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Copyright information

© Springer Science+Business Media B.V. 2011

Authors and Affiliations

  • Max García-Melchor
    • 1
  • Gregori Ujaque
    • 1
  • Feliu Maseras
    • 1
    • 2
  • Agustí Lledós
    • 1
  1. 1.Departament de Química, Edifici CnUniversitat Autònoma de BarcelonaBellaterraSpain
  2. 2.Institute of Chemical Research of Catalonia (ICIQ)TarragonaSpain

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