Room-Temperature Stille Cross-Couplings of Alkenyltin Reagents and Functionalized Alkyl Bromides that Possess β Hydrogens

Menzel, Karsten; Fu, Gregory C.

doi:10.1021/ja0344563

Cited by 138 publications

(56 citation statements)

References 19 publications

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“…With PtBu 2 Me as the ligand, substituted olefins were formed in good to very good yields in the presence of [{Pd(h-C 3 H 5 )Cl} 2 ] (2.5 mol %) and Me 4 NF (1.9 equiv). [46] Furthermore, alkyl diaminophosphines were shown to be active ligands under similar reaction conditions (Scheme 36). Although the yields were comparable to those observed for the system with PtBu 2 Me, aryl stannanes can also be used as substrates with this modified catalyst system.…”

Section: Allyl à MX Nmentioning

confidence: 96%

Catalysts for Cross‐Coupling Reactions with Non‐activated Alkyl Halides

Frisch¹,

Beller²

2005

Angew Chem Int Ed

868

280

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Despite the problems inherent to metal-catalyzed cross-coupling reactions with alkyl halides, these reactions have become increasingly important during the last few years. Detailed mechanistic investigations have led to a variety of novel procedures for the selective cross-coupling of non-activated alkyl halides bearing beta hydrogen atoms with a variety of organometallic nucleophiles under mild reaction conditions. This Minireview highlights selected examples of metal-catalyzed coupling methods and is intended to encourage chemists to exploit the potential of these approaches in organic synthesis.

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Section: Allyl à MX Nmentioning

confidence: 96%

Catalysts for Cross‐Coupling Reactions with Non‐activated Alkyl Halides

Frisch¹,

Beller²

2005

Angew Chem Int Ed

868

280

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“…[124,125] The [Pd(1,6-diene)L] complexes were found to be more effective catalysts for these reactions than mixtures of the phosphanes and Pd(OAc) 2 or [Pd 2 (dba) 3 ]. [126] The Stille coupling at room temperature of alkenyl stannanes with alkyl bromides that possess b hydrogen atoms is also possible with similar catalysts (Scheme 18), [127] although it was necessary to add a fluoride salt to promote the reactivity of the stannane. With the diaminophosphane ligand PCy(pyrrolidinyl) 2 the reaction can be extended to the coupling of aryl stannanes.…”

Section: Cross-coupling Reactions In the Presence Of Bulky Phosphanesmentioning

confidence: 99%

The Mechanisms of the Stille Reaction

2004

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Eighteen years ago in Angewandte Chemie John K. Stille reviewed a novel methodology, which eventually became known by his name, for the coupling of organostannanes with organic electrophiles. Since then that seed has blossomed into a multifaceted methodology full of hidden possibilities to explore, discover, and enjoy. Very recent modifications are making synthetic wishes come true that were only dreamed of a few years ago. Moreover, as important advances are being made in the understanding of the mechanistic details of the process, it is becoming increasingly possible to apply this essential reaction and its new variants in a less empirical way. The purpose of this Review is to give a critical account of this progress.

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“…Trialkylphosphines with bulky substituents are highly useful ligands for palladium-complex catalysts in various types of cross-coupling reactions of the Suzuki, [1][2][3][4][5][6][7][8][9][10][11] Sonogashira, [12][13][14][15][16][17][18][19][20][21] Heck, [22][23][24][25][26][27] Buchwald-Hartwig amination [28][29][30][31][32][33][34] and ether formation, [35] Negishi, [36] Stille, [37][38][39] Hiyama, [40] Kumada, [41] a-arylation, [42,43] and carbonylation type. [44] The main reasons for the favorable catalytic properties of trialkylphosphine-palladium complexes are the electron-richness and the steric bulk of trialkylphosphine ligands, which favor the formation of low-coordinate and highly active Pd complexes, possibly of the L 1 Pd type, [45][46]…”

Section: Introductionmentioning

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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Room-Temperature Stille Cross-Couplings of Alkenyltin Reagents and Functionalized Alkyl Bromides that Possess β Hydrogens

Cited by 138 publications

References 19 publications

Catalysts for Cross‐Coupling Reactions with Non‐activated Alkyl Halides

Catalysts for Cross‐Coupling Reactions with Non‐activated Alkyl Halides

The Mechanisms of the Stille Reaction

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

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