Oxidative Addition of Haloheteroarenes to Palladium(0): Concerted versus S<sub>N</sub>Ar‐Type Mechanism

Maes, Bert U. W.; Verbeeck, Stefan; Verhelst, Tom; Ekomié, Audrey; Wolff, Niklas von; Lefèvre, Guillaume; Mitchell, Emily A.; Jutand, Anny

doi:10.1002/chem.201406210

Cited by 76 publications

(112 citation statements)

References 78 publications

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“…To conclude this section, it should be noted that R‐X oxidative addition process is well‐studied computationally at various levels . The results obtained in this study are in a good general agreement with the literature data.…”

Section: Resultssupporting

confidence: 87%

Switching the nature of catalytic centers in Pd/NHC systems by solvent effect driven non‐classical R‐NHC Coupling

Gordeev

Ananikov

2018

J Comput Chem

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A well‐established oxidative addition of organic halides (R‐X) to N‐heterocyclic carbene (NHC) complexes of palladium(0) leads to formation of (NHC)(R)PdII(X)L species, the key intermediates in a large variety of synthetically useful cross‐coupling reactions. Typical consideration of the cross‐coupling catalytic cycle is based on the assumption of intrinsic stability of these species, where the subsequent steps involve coordination of the second reacting partner. Thus, high stability of the intermediate (NHC)(R)PdII(X)L species is usually taken for granted. In the present study it is discussed that such intermediates are prone to non‐classical R‐NHC intramolecular coupling process (R = Me, Ph, Vinyl, Ethynyl) that results in removal of NHC ligand and generation of another type of Pd catalytic system. DFT calculations (BP86, TPSS, PBE1PBE, B3LYP, M06, wB97X‐D) clearly show that outcome of R‐NHC coupling process is not only determined by chemical nature of the organic substituent R, but also strongly depends on the type of solvent. The reaction is most favorable in polar solvents, whereas the non‐polar solvents render the products less stable. © 2019 Wiley Periodicals, Inc.

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Section: Resultssupporting

confidence: 87%

Switching the nature of catalytic centers in Pd/NHC systems by solvent effect driven non‐classical R‐NHC Coupling

Gordeev

Ananikov

2018

J Comput Chem

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“…In the transition state [5][6][7][8][9]°,t he elongation of the PdÀC 2 bond (j DL j = 0.072 )a nd shortening of the C 2 À O 1 bond (j DL j = 1.253 )t akes place. Subsequent approacho ft he PhCl fragment to the palladium(0) species 9 leads to the formation of the pre-complex 10,w hich involves an exergonic step of 5.3 kcal mol À1 .As imilar pre-complex has been postulated by Jutand et al [52] in the oxidative addition reactionb etween PhCl and the [Pd 0 (PPh 3 ) 2 ]c atalyst. Formation of intermediate 9 leads to ad ecrease of the formal oxidation state by two units with respectt oi ntermediate 5.F urthermore, this is supported by as ignificant increase of the electron density on the Pd centre (q Pd = À0.202 e in 9 vs. 0.355 e in 5).…”

Section: Path Amentioning

confidence: 85%

Exploring the Oxidative‐Addition Pathways of Phenyl Chloride in the Presence of Pd^IIAbnormal N‐Heterocyclic Carbene Complexes: A DFT Study

Mondal

Maity

et al. 2016

Chemistry A European J

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DFT calculations were performed to elucidate the oxidative addition mechanism of the dimeric palladium(II) abnormal N-heterocyclic carbene complex 2 in the presence of phenyl chloride and NaOMe base under the framework of a Suzuki-Miyaura cross-coupling reaction. Pre-catalyst 2 undergoes facile, NaOMe-assisted dissociation, which led to monomeric palladium(II) species 5, 6, and 7, each of them independently capable of initiating oxidative addition reactions with PhCl. Thereafter, three different mechanistic routes, path a, path b, and path c, which originate from the catalytic species 5, 7, and 6, were calculated at M06-L-D3(SMD)/LANL2TZ(f)(Pd)/6-311++G**//M06-L/LANL2DZ(Pd)/6-31+G* level of theory. All studied routes suggested the rather uncommon Pd /Pd oxidative addition mechanism to be favourable under the ambient reaction conditions. Although the Pd /Pd routes are generally facile, the final reductive elimination step from the catalytic complexes were energetically formidable. The Pd /Pd activation barriers were calculated to be 11.3, 9.0, 26.7 kcal mol (ΔΔ G ) more favourable than the Pd /Pd reductive elimination routes for path a, path b, and path c, respectively. Out of all the studied pathways, path a was the most feasible as it comprised of a Pd /Pd activation barrier of 24.5 kcal mol (ΔG ). To further elucidate the origin of transition-state barriers, EDA calculations were performed for some key saddle points populating the energy profiles.

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“…Likewise, the coordination of AlMe 3 to the O in IP1 will lead to IP10 . The transition states for concerted and S N Ar mechanisms for the C–O oxidative addition of IP10 can be located, similar to those involved in carbon–halide oxidative addition . In the concerted mechanism, IP10 proceeds via TS3 to IP11 with an overall energy barrier of +38.0 kcal/mol.…”

Section: Computational Mechanistic Studiesmentioning

confidence: 79%

Nickel‐mediated cross‐coupling via C–O activation assisted by organoaluminum

Liu

Wititsuwannakul

Hsieh

et al. 2019

J Chinese Chemical Soc

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We report the alkylation and arylation cross‐coupling of aryl ethers based on C–O bond activation using a nickel catalyst and organoaluminum reagents. Ni(cod)2 in combination with 1,2‐bis(dicyclohexylphosphino)ethane ligand in toluene solution at 130°C are the best conditions. The naphthyl ether or methoxy pyridine derivatives are suitable substrates for alkylation and arylation reaction with a wider scope of aluminum reagents in good yields. Computational analysis on the pyridine substrate is provided to help delineate the mechanistic pathway and demonstrate the important aspects of the cooperative interaction bimetallic catalysis. First, the coordination of AlMe3 to the O atom of pyridine is essential for C–O activation. Second, the β‐H transfer from methoxy to pyridine could be discouraged through the use of bidentate phosphine as a ligand. Finally, excess AlMe3 reagent is critical for facilitating a reductive elimination process.

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Oxidative Addition of Haloheteroarenes to Palladium(0): Concerted versus S_NAr‐Type Mechanism

Cited by 76 publications

References 78 publications

Switching the nature of catalytic centers in Pd/NHC systems by solvent effect driven non‐classical R‐NHC Coupling

Switching the nature of catalytic centers in Pd/NHC systems by solvent effect driven non‐classical R‐NHC Coupling

Exploring the Oxidative‐Addition Pathways of Phenyl Chloride in the Presence of Pd^IIAbnormal N‐Heterocyclic Carbene Complexes: A DFT Study

Nickel‐mediated cross‐coupling via C–O activation assisted by organoaluminum

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Oxidative Addition of Haloheteroarenes to Palladium(0): Concerted versus SNAr‐Type Mechanism

Cited by 76 publications

References 78 publications

Switching the nature of catalytic centers in Pd/NHC systems by solvent effect driven non‐classical R‐NHC Coupling

Switching the nature of catalytic centers in Pd/NHC systems by solvent effect driven non‐classical R‐NHC Coupling

Exploring the Oxidative‐Addition Pathways of Phenyl Chloride in the Presence of PdIIAbnormal N‐Heterocyclic Carbene Complexes: A DFT Study

Nickel‐mediated cross‐coupling via C–O activation assisted by organoaluminum

Contact Info

Product

Resources

About

Oxidative Addition of Haloheteroarenes to Palladium(0): Concerted versus S_NAr‐Type Mechanism

Exploring the Oxidative‐Addition Pathways of Phenyl Chloride in the Presence of Pd^IIAbnormal N‐Heterocyclic Carbene Complexes: A DFT Study