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Exploiting noninnocent (E,E)-dibenzylideneacetone (dba) effects in palladium(0)-mediated cross-coupling reactions: Modulation of the electronic properties of dba affects catalyst activity and stability in ligand and ligand-free reaction systems

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Exploiting noninnocent (E,E)-dibenzylideneacetone (dba) effects in palladium(0)-mediated cross-coupling reactions: Modulation of the electronic properties of dba affects catalyst activity and stability in ligand and ligand-free reaction systems. / Fairlamb, Ian J. S.; Kapdi, Anant R.; Lee, Adam F.; McGlacken, Gerard P.; Weissburger, Felix; de Vries, Andre H. M.; Schmieder-van de Vondervoort, Lizette.

In: Chemistry - A European Journal, Vol. 12, No. 34, 24.11.2006, p. 8750-8761.

Research output: Contribution to journalArticle

Harvard

Fairlamb, IJS, Kapdi, AR, Lee, AF, McGlacken, GP, Weissburger, F, de Vries, AHM & Schmieder-van de Vondervoort, L 2006, 'Exploiting noninnocent (E,E)-dibenzylideneacetone (dba) effects in palladium(0)-mediated cross-coupling reactions: Modulation of the electronic properties of dba affects catalyst activity and stability in ligand and ligand-free reaction systems', Chemistry - A European Journal, vol. 12, no. 34, pp. 8750-8761. https://doi.org/10.1002/chem.200600473

APA

Fairlamb, I. J. S., Kapdi, A. R., Lee, A. F., McGlacken, G. P., Weissburger, F., de Vries, A. H. M., & Schmieder-van de Vondervoort, L. (2006). Exploiting noninnocent (E,E)-dibenzylideneacetone (dba) effects in palladium(0)-mediated cross-coupling reactions: Modulation of the electronic properties of dba affects catalyst activity and stability in ligand and ligand-free reaction systems. Chemistry - A European Journal, 12(34), 8750-8761. https://doi.org/10.1002/chem.200600473

Vancouver

Fairlamb IJS, Kapdi AR, Lee AF, McGlacken GP, Weissburger F, de Vries AHM et al. Exploiting noninnocent (E,E)-dibenzylideneacetone (dba) effects in palladium(0)-mediated cross-coupling reactions: Modulation of the electronic properties of dba affects catalyst activity and stability in ligand and ligand-free reaction systems. Chemistry - A European Journal. 2006 Nov 24;12(34):8750-8761. https://doi.org/10.1002/chem.200600473

Author

Fairlamb, Ian J. S. ; Kapdi, Anant R. ; Lee, Adam F. ; McGlacken, Gerard P. ; Weissburger, Felix ; de Vries, Andre H. M. ; Schmieder-van de Vondervoort, Lizette. / Exploiting noninnocent (E,E)-dibenzylideneacetone (dba) effects in palladium(0)-mediated cross-coupling reactions: Modulation of the electronic properties of dba affects catalyst activity and stability in ligand and ligand-free reaction systems. In: Chemistry - A European Journal. 2006 ; Vol. 12, No. 34. pp. 8750-8761.

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@article{bf39b32457904ed1aec414ed9726dc6c,
title = "Exploiting noninnocent (E,E)-dibenzylideneacetone (dba) effects in palladium(0)-mediated cross-coupling reactions: Modulation of the electronic properties of dba affects catalyst activity and stability in ligand and ligand-free reaction systems",
abstract = "The reactivity of palladium(0) complexes, [Pd-2(0),(dba-n,n'-Z)(3)] (n,n'-Z=4,4'-F; 4,4'-CF3; 4,4'-H; 4,4'-MeO) and [Pd-0(dba-n,n'-Z)(2)] (n,n'-Z= 4,4'-CF3; 4,4'-H; 3,3',5,5'-OMe), used as precursor catalysts with suitable donor ligands (e.g. phosphines, N-heterocyclic carbenes), has been correlated in several palladium (0)-mediated cross-coupling processes. Increasing the electron density on the aryl moiety of the dban,n'-Z ligand increases the overall catalytic activity in the majority of these processes. This effect primarily derives from destabilization of the LnPd0-eta(2)dba interaction (in d pi-pi* synergic bonding, n = 1 or 2), which ultimately increases the global concentration of catalytically active L,,Pd' available for reaction with aryl halide in the first committed step in the general catalytic cycle(s) (oxidative addition). Decreasing electron density on the aryl moiety of the dba-n,n'-Z ligand stabilizes the Pd-0-eta(2)-dba interaction, reducing catalytic activity. The specific type of dban,n'-Z ligand appears to also play a stabilizing role in the catalytic cycle, preventing I'd agglomeration, and increasing catalyst longevity. A subtle balance therefore exists between the LnPd0 concentration (and the associated catalytic activity) and catalyst longevity. Changing the type of dba-n,n'-Z ligand controls the concentration of LnPd0 and the rate of the oxidative addition step, and not other intimate steps within the catalytic cycle(s), for example, transmetallation (or carbopalladation) and reductive elimination. The role of dban,n'-Z ligands in Heck arylation is more convoluted and dependant on the alkene substrate employed, although trends have emerged. Changes in the structure of dba-n,n'-Z had a minimal affect on Buchwald-Hartwig aryl amination processes. A secondary Michael reaction of dba-n,n'-Z with amine and/ or base effectively lessens its interference in the catalytic cycle.",
keywords = "arylation, C-C coupling, homogeneous catalysis, kinetics, palladium, GENERATED IN-SITU, HETEROCYCLIC CARBENE COMPLEXES, ARYL HALIDES, SUZUKI-MIYAURA, OXIDATIVE ADDITION, ALPHA-ARYLATION, HECK REACTIONS, STRUCTURAL-CHARACTERIZATION, ORGANIC ELECTROPHILES, PALLADIUM CATALYSIS",
author = "Fairlamb, {Ian J. S.} and Kapdi, {Anant R.} and Lee, {Adam F.} and McGlacken, {Gerard P.} and Felix Weissburger and {de Vries}, {Andre H. M.} and {Schmieder-van de Vondervoort}, Lizette",
year = "2006",
month = "11",
day = "24",
doi = "10.1002/chem.200600473",
language = "English",
volume = "12",
pages = "8750--8761",
journal = "Chemistry : A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "34",

}

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TY - JOUR

T1 - Exploiting noninnocent (E,E)-dibenzylideneacetone (dba) effects in palladium(0)-mediated cross-coupling reactions: Modulation of the electronic properties of dba affects catalyst activity and stability in ligand and ligand-free reaction systems

AU - Fairlamb, Ian J. S.

AU - Kapdi, Anant R.

AU - Lee, Adam F.

AU - McGlacken, Gerard P.

AU - Weissburger, Felix

AU - de Vries, Andre H. M.

AU - Schmieder-van de Vondervoort, Lizette

PY - 2006/11/24

Y1 - 2006/11/24

N2 - The reactivity of palladium(0) complexes, [Pd-2(0),(dba-n,n'-Z)(3)] (n,n'-Z=4,4'-F; 4,4'-CF3; 4,4'-H; 4,4'-MeO) and [Pd-0(dba-n,n'-Z)(2)] (n,n'-Z= 4,4'-CF3; 4,4'-H; 3,3',5,5'-OMe), used as precursor catalysts with suitable donor ligands (e.g. phosphines, N-heterocyclic carbenes), has been correlated in several palladium (0)-mediated cross-coupling processes. Increasing the electron density on the aryl moiety of the dban,n'-Z ligand increases the overall catalytic activity in the majority of these processes. This effect primarily derives from destabilization of the LnPd0-eta(2)dba interaction (in d pi-pi* synergic bonding, n = 1 or 2), which ultimately increases the global concentration of catalytically active L,,Pd' available for reaction with aryl halide in the first committed step in the general catalytic cycle(s) (oxidative addition). Decreasing electron density on the aryl moiety of the dba-n,n'-Z ligand stabilizes the Pd-0-eta(2)-dba interaction, reducing catalytic activity. The specific type of dban,n'-Z ligand appears to also play a stabilizing role in the catalytic cycle, preventing I'd agglomeration, and increasing catalyst longevity. A subtle balance therefore exists between the LnPd0 concentration (and the associated catalytic activity) and catalyst longevity. Changing the type of dba-n,n'-Z ligand controls the concentration of LnPd0 and the rate of the oxidative addition step, and not other intimate steps within the catalytic cycle(s), for example, transmetallation (or carbopalladation) and reductive elimination. The role of dban,n'-Z ligands in Heck arylation is more convoluted and dependant on the alkene substrate employed, although trends have emerged. Changes in the structure of dba-n,n'-Z had a minimal affect on Buchwald-Hartwig aryl amination processes. A secondary Michael reaction of dba-n,n'-Z with amine and/ or base effectively lessens its interference in the catalytic cycle.

AB - The reactivity of palladium(0) complexes, [Pd-2(0),(dba-n,n'-Z)(3)] (n,n'-Z=4,4'-F; 4,4'-CF3; 4,4'-H; 4,4'-MeO) and [Pd-0(dba-n,n'-Z)(2)] (n,n'-Z= 4,4'-CF3; 4,4'-H; 3,3',5,5'-OMe), used as precursor catalysts with suitable donor ligands (e.g. phosphines, N-heterocyclic carbenes), has been correlated in several palladium (0)-mediated cross-coupling processes. Increasing the electron density on the aryl moiety of the dban,n'-Z ligand increases the overall catalytic activity in the majority of these processes. This effect primarily derives from destabilization of the LnPd0-eta(2)dba interaction (in d pi-pi* synergic bonding, n = 1 or 2), which ultimately increases the global concentration of catalytically active L,,Pd' available for reaction with aryl halide in the first committed step in the general catalytic cycle(s) (oxidative addition). Decreasing electron density on the aryl moiety of the dba-n,n'-Z ligand stabilizes the Pd-0-eta(2)-dba interaction, reducing catalytic activity. The specific type of dban,n'-Z ligand appears to also play a stabilizing role in the catalytic cycle, preventing I'd agglomeration, and increasing catalyst longevity. A subtle balance therefore exists between the LnPd0 concentration (and the associated catalytic activity) and catalyst longevity. Changing the type of dba-n,n'-Z ligand controls the concentration of LnPd0 and the rate of the oxidative addition step, and not other intimate steps within the catalytic cycle(s), for example, transmetallation (or carbopalladation) and reductive elimination. The role of dban,n'-Z ligands in Heck arylation is more convoluted and dependant on the alkene substrate employed, although trends have emerged. Changes in the structure of dba-n,n'-Z had a minimal affect on Buchwald-Hartwig aryl amination processes. A secondary Michael reaction of dba-n,n'-Z with amine and/ or base effectively lessens its interference in the catalytic cycle.

KW - arylation

KW - C-C coupling

KW - homogeneous catalysis

KW - kinetics

KW - palladium

KW - GENERATED IN-SITU

KW - HETEROCYCLIC CARBENE COMPLEXES

KW - ARYL HALIDES

KW - SUZUKI-MIYAURA

KW - OXIDATIVE ADDITION

KW - ALPHA-ARYLATION

KW - HECK REACTIONS

KW - STRUCTURAL-CHARACTERIZATION

KW - ORGANIC ELECTROPHILES

KW - PALLADIUM CATALYSIS

U2 - 10.1002/chem.200600473

DO - 10.1002/chem.200600473

M3 - Article

VL - 12

SP - 8750

EP - 8761

JO - Chemistry : A European Journal

JF - Chemistry : A European Journal

SN - 0947-6539

IS - 34

ER -