Suzuki cross-coupling of arylboronic acids mediated by a hydrosoluble Pd(0)/TPPTS catalyst

Dupuis, Christophe; Adiey, Kouacou; Charruault, Lise; Michelet, Véronique; Savignac, Monique; Genêt, Jean‐Pierre

doi:10.1016/s0040-4039(01)01301-6

Cited by 131 publications

(41 citation statements)

References 16 publications

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“…[87,88] Only a few examples of aqueous Suzuki coupling of aryl chlorides have been described, notable in this respect are recent publications by Buchwald et al [89,90] and Fu et al [11] who report on the facile Suzuki coupling in water and water/dioxane for a broad range of substrates. [4,[91][92][93] Consequently, to render the 9-fluorenylphos- www.chemeurj.org phines water soluble, the aromatic ring was sulfonated by treatment of the phosphonium salt 17 c with concentrated sulphuric acid, resulting in the formation of the respective 2-sulfonated fluorene in 77 % yield (Scheme 5). We studied a range of different aryl bromides and aryl chlorides in Suzuki coupling reactions by using 4-tolueneboronic acid, 1-naphthylboronic acid, and 3-pyridylboronic acids (Table 7).…”

Section: Resultsmentioning

confidence: 99%

9‐Fluorenylphosphines for the Pd‐Catalyzed Sonogashira, Suzuki, and Buchwald–Hartwig Coupling Reactions in Organic Solvents and Water

Fleckenstein

Plenio

2007

Chemistry A European J

173

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The lithiation/alkylation of fluorene leads to various 9-alkyl-fluorenes (alkyl=Me, Et, iPr, -Pr, -C18H25) in>95% yields, for which lithiation and reaction with R2PCl (R=Cy, iPr, tBu) generates 9-alkyl, 9-PR2-fluorenes which constitute electron-rich and bulky phosphine ligands. The in-situ-formed palladium-phosphine complexes ([Na2PdCl4], phosphonium salt, base, substrates) were tested in the Sonogashira, Suzuki, and Buchwald-Hartwig reactions of aryl chlorides and aryl bromides in organic solvents. The Sonogashira coupling of aryl chlorides at 100-120 degrees C leads to>90% yields with 1 mol% of Pd catalyst. The Suzuki coupling of aryl chlorides typically requires 0.05 mol% of Pd catalyst at 100 degrees C in dioxane for quantitative product formation. To carry out "green" cross-coupling reactions in water, 9-ethylfluorenyldicyclohexylphosphine was reacted in sulphuric acid to generate the respective 2-sulfonated phosphonium salt. The Suzuki coupling of activated aryl chlorides by using this water-soluble catalyst requires only 0.01 mol% of Pd catalyst, while a wide range of aryl chlorides can be quantitatively converted into the respective coupling products by using 0.1-0.5 mol% of catalyst in pure water at 100 degrees C. Difficult substrate combinations, such as naphthylboronic acid or 3-pyridylboronic acid and aryl chlorides are coupled at 100 degrees C by using 0.1-0.5 mol% of catalyst in pure water to obtain the respective N-heterocycles in quantitative yields. The copper-free aqueous Sonogashira coupling of aryl bromides generates the respective tolane derivatives in>95% yield.

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Section: Resultsmentioning

confidence: 99%

9‐Fluorenylphosphines for the Pd‐Catalyzed Sonogashira, Suzuki, and Buchwald–Hartwig Coupling Reactions in Organic Solvents and Water

Fleckenstein

Plenio

2007

Chemistry A European J

173

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“…Suzuki-Miyaura cross-coupling reactions between a range of aryl bromides and boronic compounds can be performed under mild conditions with high efficiencies and turnover numbers. [48] The process toler- ates electron-rich and electron-poor substituents and provides an efficient access to sterically hindered biaryls (Scheme 12). This TPPTS/Pd(OAc) 2 catalyst system has been applied to the synthesis of Xenalipin, a potential cholesterol-reducing drug (Scheme 13).…”

Section: Suzuki-miyaura Coupling With Water-soluble Phosphines As Ligandmentioning

confidence: 99%

Suzuki–Miyaura Cross‐Coupling Reactions in Aqueous Media: Green and Sustainable Syntheses of Biaryls

Polshettiwar¹,

Decottignies²,

Len³

et al. 2010

ChemSusChem

342

154

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Carbon-carbon cross-coupling reactions are among the most important processes in organic chemistry, and Suzuki-Miyaura reactions are among the most widely used protocols for the formation of carbon-carbon bonds. These reactions are generally catalyzed by soluble palladium complexes with various ligands. However, the use of toxic organic solvents remains a scientific challenge and an aspect of economical and ecological relevance. This Review will summarize various recently developed significant methods by which the Suzuki-Miyaura coupling was conducted in aqueous media, and analyzes if they are "real green" protocols.

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“…76 Additional studies indicated that the SM cross-coupling can be extended efficiently to a range of aryl bromides and arylboronic acids using a water-soluble Pd(0)/TPPTS catalyst under mild reaction conditions (Scheme 31). 77 This procedure has been extended to electron-rich and electron-poor substrates and provides an easy access to sterically hindered biaryls having three ortho-substituents with good ton. 78 The catalyst can be recycled three times without loss of activity.…”

Section: Two-phase Sm Cross-coupling Reactions With Watersoluble Pallmentioning

confidence: 99%

Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis

Kotha¹,

Lahiri²,

Kashinath³

2002

Tetrahedron

1,659

530

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Suzuki cross-coupling of arylboronic acids mediated by a hydrosoluble Pd(0)/TPPTS catalyst

Cited by 131 publications

References 16 publications

9‐Fluorenylphosphines for the Pd‐Catalyzed Sonogashira, Suzuki, and Buchwald–Hartwig Coupling Reactions in Organic Solvents and Water

9‐Fluorenylphosphines for the Pd‐Catalyzed Sonogashira, Suzuki, and Buchwald–Hartwig Coupling Reactions in Organic Solvents and Water

Suzuki–Miyaura Cross‐Coupling Reactions in Aqueous Media: Green and Sustainable Syntheses of Biaryls

Recent applications of the Suzuki–Miyaura cross-coupling reaction in organic synthesis

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