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An Asymmetric Suzuki-Miyaura Reaction Mechanism

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

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Abstract

The Suzuki-Miyaura reaction, commonly known simply as Suzuki coupling, is one of the most practiced types of C–C cross-coupling reactions. In 2008, the group of Profs. Fern\(\acute{\mathrm{a}}\)ndez and Lassaletta reported that the use of the (S,S)-2,5-diphenyl-pyrrolidine-derived glyoxal bis-hydrazone ligand in catalysts of the type [PdCl\(_2\)(L)] in conjunction with Cs\(_2\)CO\(_3\) as base and toluene as solvent, allows the asymmetric Suzuki-Miyaura coupling of a broad variety of substrates in high yields and enantioselectivities. Motivated by these striking results, we decided to investigate theoretically the reported Suzuki-Miyaura coupling that led to the highest yield and enantioselectivity. The major objective of this theoretical study is to give an explanation of the origin of the enantioselectivities experimentally observed. With this aim, the full catalytic cycle for the above mentioned coupling was computed. All the results of obtained in this work are presented in this chapter. This work has been carried out in collaboration with the experimental group of Profs. Rosario Fern\(\acute{\mathrm{a}}\)ndez and J. M. Lassaletta from the Universidad de Sevilla and the CSIC de Sevilla, respectively.

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Notes

  1. 1.

    The theoretical results obtained with this model system remained qualitatively valid when the PH\(_3\) ligands and the vinyl groups were replaced by the commonly used PPh\(_3\) ligands and phenyl groups [18], respectively. Importantly, in the transmetalation with phenyl groups, the reaction from S-3 was found to take place in one transition state instead of in two (i.e. S-TS2 and S-TS3).

  2. 2.

    As we will see later, this was assumed in the asymmetric Suzuki-Miyaura reaction investigated in this thesis.

  3. 3.

    The same coupling was also carried out at \(80\,^\circ \mathrm{{C}}\) affording the (R)-product at a higher yield (i.e. 98 %) but with a lower ee (i.e. 90 % (R)).

  4. 4.

    For further details on this model, see the last section of Chap. 2.

  5. 5.

    The nomenclature adopted for these \(\eta ^{2}\)-coordination modes is the one according to the IUPAC nomenclature for polycyclic aromatic hydrocarbons. For simplicity, we denoted the \(\eta ^{2}\)-j coordination in the different intermediates shown in Fig. 6.5 by adding a prime symbol (\(^{\prime }\)) to their names.

  6. 6.

    The transition state starting from OAA-I1 and OAB-I1 \(^\prime \) intermediates could not be located. Additional calculations are currently underway.

  7. 7.

    This does not happen in the cases in which the tail of 3 is below the plain defined by Pd and their coordinated ligands, as the \(\eta ^{2}\)-coordination that results from TBa-TS1 is already the appropriate \(\eta ^{2}\)-b coordination required in TBa-TS2. Hence, in the A-anti and B-syn routes no coordination change is needed and, accordingly, the transmetalation takes place directly from TBa-I2 via the transition state TBa-TS2. In contrast, in the A-syn route the transmetalation occurs in the same way than in the B-anti route.

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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). An Asymmetric Suzuki-Miyaura Reaction Mechanism. 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_6

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