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General Introduction

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A Theoretical Study of Pd-Catalyzed C-C Cross-Coupling Reactions

Part of the book series: Springer Theses ((Springer Theses))

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Abstract

As the title above suggests, this first chapter is devoted to make a general introduction to the main topic of this present thesis: the Pd-catalyzed cross-coupling reactions. With this aim, in the first part of this chapter the concept of catalysis, its origin, as well as other related topics will be briefly introduced. Next, in the second part of this chapter, the definition of C–C cross-coupling reactions and a summary of their generally accepted reaction pathway will be presented. Finally, the elementary steps that take part in this type of reactions will be described separately. Furthermore, for each of these steps, the most relevant mechanistic studies on Pd-catalyzed C–C cross-coupling reactions reported in the last years, with particular attention to the theoretical ones, will be reviewed. In principle, all the concepts provided in this first chapter should be more than enough to contextualize all the results obtained in the course of this thesis, and that are presented in Chaps. 4, 5 and 6.

In all science, error precedes the truth, and it is better it should go first than last. Hugh Walpole.

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Notes

  1. 1.

    The word “catalysis” originates from the Greek words “\(\kappa \alpha \tau \acute{\alpha }\)” and “\(\lambda \acute{\upsilon }\sigma \iota \varsigma \)” and has the sense of “dissolution”.

  2. 2.

    Wilhelm Ostwald was awarded with the Nobel Prize in Chemistry in 1909 “in recognition of his work on catalysis and for his investigations into the fundamental principles governing chemical equilibria and rates of reaction”.

  3. 3.

    Although this expression applies only to gas phase reactions, it is often applied in general.

  4. 4.

    The homocoupling is the coupling of two identical molecules.

  5. 5.

    Richard F. Heck, Ei-ichi Negishi and Akira Suzuki shared the Nobel Prize in Chemistry in 2010 “for palladium-catalyzed cross couplings in organic synthesis”. These scientists are the developers of the widely known Heck, Negishi, and Suzuki reactions, respectively.

  6. 6.

    These trends are only given by way of guidance; there may be exceptions.

  7. 7.

    This may be governed by the trans-effect.

    Trans-effect: is the effect that produces a ligand that facilitates the exchange or substitution of a second ligand that is in trans position respect to the former. We refer to ligands with high trans-effect when these facilitate that substitution.

  8. 8.

    There is also another variant of radical mechanism called chain mechanism. This, however, will not be discussed here. More details on this type of mechanism can be found in books on general organometallic chemistry [7, 91].

  9. 9.

    The reverse of the transmetalation reaction is commonly known as “retrotransmetalation” [74].

  10. 10.

    As in oxidative addition, these trends are only given by way of guidance, because always there may be exceptions.

  11. 11.

    This principle holds that a reversible reaction proceeds by the same mechanism in both forward and reverse directions.

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  1. Department of Chemistry, Autonomous University of Barcelona, Edifici Cn, 08193, Cerdanyola del Vallès, Spain

    Max García Melchor

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García Melchor, M. (2013). General Introduction. In: A Theoretical Study of Pd-Catalyzed C-C Cross-Coupling Reactions. Springer Theses. Springer, Cham. https://doi.org/10.1007/978-3-319-01490-6_1

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