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Theoretical Evaluation of Phosphine Effects in Cross-Coupling Reactions

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Phosphorus Compounds

Part of the book series: Catalysis by Metal Complexes ((CMCO,volume 37))

Abstract

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.

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Notes

  1. 1.

    For Pd complexes containing the ligand L = PCy3, Hartwig et al. concluded that the reaction would take place from Pd(PCy3)3 (the major species under reaction conditions) via reversible dissociation of one phosphine ligand to generate the Pd(PCy3)2 species. Then, this species would react irreversibly with PhI. However, the mechanism for this reaction could not be confirmed whether it would occur through either the pathway A or the pathway B.

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Acknowledgments

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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  1. Departament de Química, Edifici Cn, Universitat Autònoma de Barcelona, 08193, Bellaterra, Catalonia, Spain

    Max García-Melchor, Gregori Ujaque, Feliu Maseras & Agustí Lledós

  2. Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans, 16, 43007, Tarragona, Catalonia, Spain

    Feliu Maseras

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  3. Feliu Maseras
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  4. Agustí Lledós
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Editors and Affiliations

  1. Istituto di Chimica dei Composti, Organometallici (ICCOM), CNR Firenze, Via Madonna del Piano 10, Sesto Fiorentino, 50019, Firenze, Italy

    Maurizio Peruzzini

  2. Istituto di Chimica dei Composti, Organometallici (ICCOM), CNR Firenze, Via Madonna del Piano 10, Sesto Fiorentino, 50019, Firenze, Italy

    Luca Gonsalvi

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© 2011 Springer Science+Business Media B.V.

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García-Melchor, M., Ujaque, G., Maseras, F., Lledós, A. (2011). Theoretical Evaluation of Phosphine Effects in Cross-Coupling Reactions. In: Peruzzini, M., Gonsalvi, L. (eds) Phosphorus Compounds. Catalysis by Metal Complexes, vol 37. Springer, Dordrecht. https://doi.org/10.1007/978-90-481-3817-3_3

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