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    Mechanism of the Suzuki–Miyaura Cross-Coupling Reaction Mediated by [Pd(NHC)(allyl)Cl] Precatalysts

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    Type
    Article
    Authors
    Meconi, Giulia Magi
    Vummaleti, Sai V. C. cc
    Luque-Urrutia, Jesús Antonio
    Belanzoni, Paola cc
    Nolan, Steven P. cc
    Jacobsen, Heiko cc
    Cavallo, Luigi cc
    Solà, Miquel cc
    Poater, Albert cc
    KAUST Department
    Chemical Science Program
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    KAUST Grant Number
    OSR-2015-CCF-1974-03
    Date
    2017-05-24
    Online Publication Date
    2017-05-24
    Print Publication Date
    2017-06-12
    Embargo End Date
    2018-05-24
    Permanent link to this record
    http://hdl.handle.net/10754/625104
    
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    Abstract
    Density functional theory calculations have been used to investigate the activation mechanism for the precatalyst series [Pd]-X-1–4 derived from [Pd(IPr)(R-allyl)X] species by substitutions at the terminal position of the allyl moiety ([Pd] = Pd(IPr); R = H (1), Me (2), gem-Me2 (3), Ph (4), X = Cl, Br). Next, we have investigated the Suzuki–Miyaura cross-coupling reaction for the active catalyst species IPr-Pd(0) using 4-chlorotoluene and phenylboronic acid as substrates and isopropyl alcohol as a solvent. Our theoretical findings predict an upper barrier trend, corresponding to the activation mechanism for the [Pd]-Cl-1–4 series, in good agreement with the experiments. They indeed provide a quantitative explanation of the low yield (12%) displayed by [Pd]-Cl-1 species (ΔG⧧ ≈ 30.0 kcal/mol) and of the high yields (≈90%) observed in the case of [Pd]-Cl-2–4 complexes (ΔG⧧ ≈ 20.0 kcal/mol). Additionally, the studied Suzuki–Miyaura reaction involving the IPr-Pd(0) species is calculated to be thermodynamically favorable and kinetically facile. Similar investigations for the [Pd]-Br-1–4 series, derived from [Pd(IPr)(R-allyl)Br], indicate that the oxidative addition step for IPr-Pd(0)-mediated catalysis with 4-bromotoluene is kinetically more favored than that with 4-chlorotoluene. Finally, we have explored the potential of Ni-based complexes [Ni((IPr)(R-allyl)X] (X = Cl, Br) as Suzuki–Miyaura reaction catalysts. Apart from a less endergonic reaction energy profile for both precatalyst activation and catalytic cycle, a steep increase in the predicted upper energy barriers (by 2.0–15.0 kcal/mol) is calculated in the activation mechanism for the [Ni]-X-1–4 series compared to the [Pd]-X-1–4 series. Overall, these results suggest that Ni-based precatalysts are expected to be less active than the Pd-based precatalysts for the studied Suzuki–Miyaura reaction.
    Citation
    Meconi GM, Vummaleti SVC, Luque-Urrutia JA, Belanzoni P, Nolan SP, et al. (2017) Mechanism of the Suzuki–Miyaura Cross-Coupling Reaction Mediated by [Pd(NHC)(allyl)Cl] Precatalysts. Organometallics 36: 2088–2095. Available: http://dx.doi.org/10.1021/acs.organomet.7b00114.
    Sponsors
    A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN. M.S. thanks EU for a FEDER fund (UNGI08-4E-003), the Generalitat de Catalunya for project 2014SGR931 and ICREA Academia 2014 prize, and MINECO of Spain through project CTQ2014-54306-P. G.M.M. thanks LLP/Erasmus Student Placement Programme (A.A. 2012/2013) for funding. S.P.N. acknowledges the ERC for support of this work. This publication is based upon work supported by the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under Award No. OSR-2015-CCF-1974-03. We thank the referees for helpful comments and suggestions.
    Publisher
    American Chemical Society (ACS)
    Journal
    Organometallics
    DOI
    10.1021/acs.organomet.7b00114
    Additional Links
    http://pubs.acs.org/doi/abs/10.1021/acs.organomet.7b00114
    https://dugi-doc.udg.edu/bitstream/10256/14359/1/AM-ReactionMechanism.pdf
    ae974a485f413a2113503eed53cd6c53
    10.1021/acs.organomet.7b00114
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

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