Catalytic activity of Pd(II) and Pd(II)/DAB-R systems for the Heck arylation of olefins

Gabriela A. Grasa; Rohit Singh; Edwin D. Stevens; Steven P. Nolan

doi:10.1016/S0022-328X(03)00375-9

Catalytic activity of Pd(II) and Pd(II)/DAB-R systems for the Heck arylation of olefins

Gabriela A. Grasa, Rohit Singh, Edwin D. Stevens, Steven P. Nolan

Research output: Contribution to journal › Article › peer-review

123 Scopus citations

Abstract

Palladium-catalyzed reactions of aryl bromides with various olefins involving Pd(II)/diazabutadiene (DAB-R) systems have been investigated. The scope of a coupling process using Pd(II) sources and an α-diimine as ligand in the presence of Cs₂CO₃ as base was tested using various substrates. The Pd(OAc)₂/ DAB-Cy (1, DAB-Cy=1,4-dicyclohexyl-diazabutadiene) system presents the highest activity with respect to electron-neutral and electron-deficient aryl bromides in coupling with electron rich olefins. The synthesis and X-ray characterization of a Pd(II)-diazabutadiene ligand is reported. Extensive optimization experiments showed that another Pd(II) source, Pd(acac)₂ (acac=acetylacetonate), proved to activate aryl bromides at high temperatures, low catalyst loadings when the appropriate concentration of ⁿBu₄NBr additive was employed. The effect of the DAB-Cy ligand is important at very low catalyst loadings and high temperatures. Pd(acac)₂ and Pd(acac)₂ /DAB-Cy precatalysts were very effective for the arylation of various olefins with aryl bromides with respect to reaction rate, catalyst loadings, and functional group tolerance.

Original language	English (US)
Pages (from-to)	269-279
Number of pages	11
Journal	Journal of Organometallic Chemistry
Volume	687
Issue number	2
DOIs	https://doi.org/10.1016/S0022-328X(03)00375-9
State	Published - Dec 7 2003
Externally published	Yes

Bibliographical note

Funding Information:
We gratefully acknowledge financial support from the National Science Foundation, the Petroleum Research Fund administered by ACS and the Louisiana Board of Regents. We thank OMG for the generous gift of Pd(acac) 2 .

Keywords

Diazabutadienes
Heck coupling
Palladium

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10.1016/S0022-328X(03)00375-9

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title = "Catalytic activity of Pd(II) and Pd(II)/DAB-R systems for the Heck arylation of olefins",

abstract = "Palladium-catalyzed reactions of aryl bromides with various olefins involving Pd(II)/diazabutadiene (DAB-R) systems have been investigated. The scope of a coupling process using Pd(II) sources and an α-diimine as ligand in the presence of Cs2CO3 as base was tested using various substrates. The Pd(OAc)2/ DAB-Cy (1, DAB-Cy=1,4-dicyclohexyl-diazabutadiene) system presents the highest activity with respect to electron-neutral and electron-deficient aryl bromides in coupling with electron rich olefins. The synthesis and X-ray characterization of a Pd(II)-diazabutadiene ligand is reported. Extensive optimization experiments showed that another Pd(II) source, Pd(acac)2 (acac=acetylacetonate), proved to activate aryl bromides at high temperatures, low catalyst loadings when the appropriate concentration of nBu4NBr additive was employed. The effect of the DAB-Cy ligand is important at very low catalyst loadings and high temperatures. Pd(acac)2 and Pd(acac)2 /DAB-Cy precatalysts were very effective for the arylation of various olefins with aryl bromides with respect to reaction rate, catalyst loadings, and functional group tolerance.",

keywords = "Diazabutadienes, Heck coupling, Palladium",

author = "Grasa, {Gabriela A.} and Rohit Singh and Stevens, {Edwin D.} and Nolan, {Steven P.}",

note = "Funding Information: We gratefully acknowledge financial support from the National Science Foundation, the Petroleum Research Fund administered by ACS and the Louisiana Board of Regents. We thank OMG for the generous gift of Pd(acac) 2 .",

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T1 - Catalytic activity of Pd(II) and Pd(II)/DAB-R systems for the Heck arylation of olefins

AU - Grasa, Gabriela A.

AU - Singh, Rohit

AU - Stevens, Edwin D.

AU - Nolan, Steven P.

N1 - Funding Information: We gratefully acknowledge financial support from the National Science Foundation, the Petroleum Research Fund administered by ACS and the Louisiana Board of Regents. We thank OMG for the generous gift of Pd(acac) 2 .

PY - 2003/12/7

Y1 - 2003/12/7

N2 - Palladium-catalyzed reactions of aryl bromides with various olefins involving Pd(II)/diazabutadiene (DAB-R) systems have been investigated. The scope of a coupling process using Pd(II) sources and an α-diimine as ligand in the presence of Cs2CO3 as base was tested using various substrates. The Pd(OAc)2/ DAB-Cy (1, DAB-Cy=1,4-dicyclohexyl-diazabutadiene) system presents the highest activity with respect to electron-neutral and electron-deficient aryl bromides in coupling with electron rich olefins. The synthesis and X-ray characterization of a Pd(II)-diazabutadiene ligand is reported. Extensive optimization experiments showed that another Pd(II) source, Pd(acac)2 (acac=acetylacetonate), proved to activate aryl bromides at high temperatures, low catalyst loadings when the appropriate concentration of nBu4NBr additive was employed. The effect of the DAB-Cy ligand is important at very low catalyst loadings and high temperatures. Pd(acac)2 and Pd(acac)2 /DAB-Cy precatalysts were very effective for the arylation of various olefins with aryl bromides with respect to reaction rate, catalyst loadings, and functional group tolerance.

AB - Palladium-catalyzed reactions of aryl bromides with various olefins involving Pd(II)/diazabutadiene (DAB-R) systems have been investigated. The scope of a coupling process using Pd(II) sources and an α-diimine as ligand in the presence of Cs2CO3 as base was tested using various substrates. The Pd(OAc)2/ DAB-Cy (1, DAB-Cy=1,4-dicyclohexyl-diazabutadiene) system presents the highest activity with respect to electron-neutral and electron-deficient aryl bromides in coupling with electron rich olefins. The synthesis and X-ray characterization of a Pd(II)-diazabutadiene ligand is reported. Extensive optimization experiments showed that another Pd(II) source, Pd(acac)2 (acac=acetylacetonate), proved to activate aryl bromides at high temperatures, low catalyst loadings when the appropriate concentration of nBu4NBr additive was employed. The effect of the DAB-Cy ligand is important at very low catalyst loadings and high temperatures. Pd(acac)2 and Pd(acac)2 /DAB-Cy precatalysts were very effective for the arylation of various olefins with aryl bromides with respect to reaction rate, catalyst loadings, and functional group tolerance.

KW - Diazabutadienes

KW - Heck coupling

KW - Palladium

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ER -

Catalytic activity of Pd(II) and Pd(II)/DAB-R systems for the Heck arylation of olefins

Abstract

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