scholarly journals Tetrabutylphosphonium 4-ethoxyvalerate as a biomass-originated media for homogeneous palladium-catalyzed Hiyama coupling reactions

2020 ◽  
Vol 74 (12) ◽  
pp. 4593-4598
Author(s):  
László Orha ◽  
Ábrahám Papp ◽  
József M. Tukacs ◽  
László Kollár ◽  
László T. Mika
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Functional Group ◽  
Cross Coupling ◽  
Catalyst System ◽  
Catalyst Precursor ◽  
Coupling Reactions ◽  
Tetrabutylammonium Fluoride ◽  
Carbon Carbon Bonds ◽  
Palladium Catalyzed

Abstract The introduction of a biomass-derived ionic liquid into the Hiyama coupling reactions, which has been considered as a powerful tool for the synthesis of symmetrically and non-symmetrically substituted biaryl structures, could further control or even reduce the environmental impact of this transformation. It was shown that tetrabutylphosphonium 4-ethoxyvalerate, a γ-valerolactone-based ionic liquid, can be utilized as an alternative solvent to create carbon–carbon bonds between aryl iodides and functionalized organosilanes in the presence of 1 mol% Pd under typical Hiyama conditions (130 °C, 24 h, tetrabutylammonium fluoride activator). A comparison of different ionic liquids was performed, and the effects of the catalyst precursor and the moisture content of the reaction mixture on the activity of the catalyst system were investigated. The functional group tolerance was also studied, resulting in 15 cross-coupling products (3a–o) with isolated yields of 45–72% and excellent purity (> 98%).

scholarly journals Palladium-catalyzed Sonogashira coupling reactions in γ-valerolactone-based ionic liquids

2019 ◽  
Vol 15 ◽  
pp. 2907-2913 ◽  
Author(s):  
László Orha ◽  
József M Tukacs ◽  
László Kollár ◽  
László T Mika
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Reaction Medium ◽  
Cross Coupling ◽  
Environmental Efficiency ◽  
Coupling Reactions ◽  
Sonogashira Coupling ◽  
Mild Conditions ◽  
Palladium Catalyzed ◽  
Alternative Reaction Medium

It was demonstrated that the γ-valerolactone-based ionic liquid, tetrabutylphosphonium 4-ethoxyvalerate as a partially bio-based solvent can be utilized as alternative reaction medium for copper- and auxiliary base-free Pd-catalyzed Sonogashira coupling reactions of aryl iodides and functionalized acetylenes under mild conditions. Twenty-two cross-coupling products were isolated with good to excellent yields (72–99%) and purity (>98%). These results represent an example which proves that biomass-derived safer solvents can be utilized efficiently in common, industrially important transformations exhibiting higher chemical and environmental efficiency.

Dual Nickel/Palladium-Catalyzed Reductive Cross-Coupling Reactions Between Two Phenol Derivatives

2020 ◽  
Author(s):  
Baojian Xiong ◽  
Yue Li ◽  
Yin Wei ◽  
Søren Kramer ◽  
Zhong Lian
Keyword(s):  
Functional Group ◽  
Low Cost ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Phenol Derivatives ◽  
Cross Coupling Reactions ◽  
Palladium Catalyzed ◽  
One Step ◽  
Aryl Tosylates ◽  
Low Sensitivity

Cross-coupling between substrates that can be easily derived from phenols is highly attractive due to the abundance and low cost of phenols. Here, we report a dual nickel/palladium-catalyzed reductive cross-coupling between aryl tosylates and aryl triflates; both substrates can be accessed in just one step from readily available phenols. The reaction has a broad functional group tolerance and substrate scope (>60 examples). Furthermore, it displays low sensitivity to steric effects demonstrated by the synthesis of a 2,2’disubstituted biaryl and a fully substituted aryl product. The widespread presence of phenols in natural products and pharmaceuticals allow for straightforward late-stage functionalization, illustrated with examples such as Ezetimibe and tyrosine. NMR spectroscopy and DFT calculations indicate that the nickel catalyst is responsible for activating the aryl triflate, while the palladium catalyst preferentially reacts with the aryl tosylate.

Base-Free Synthesis and Synthetic Application of Novel 3-(organochalcogenyl)prop-2-yn-1-yl Esters: Promising Anticancer Agents

Synthesis ◽  
2021 ◽  
Author(s):  
Fabiane Gritzenco ◽  
Jean Carlo Kazmierczak ◽  
Thiago Anjos ◽  
Adriane Sperança ◽  
Maura Luise Bruckchem Peixoto ◽  
...  
Keyword(s):  
Anticancer Agents ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Chalcogen Bond ◽  
Cross Coupling Reactions ◽  
Air Atmosphere ◽  
Carbon Carbon Bonds ◽  
Palladium Catalyzed ◽  
Synthetic Application

This manuscript portrays the CuI-catalyzed Csp-chalcogen bond formation through cross-coupling reactions of propynyl esters and diorganyl dichalcogenides by using DMSO as solvent, at room temperature, under base-free and open-to-air atmosphere. Generally, the reactions have proceeded very smoothly, being tolerant to range of substituents present in both substrates, affording the novel 3-(organochalcogenyl)prop-2-yn-1-yl esters in moderate to good yields. Noteworthy, the 3-(butylselanyl)prop-2-yn-1-yl benzoate proved to be useful as synthetic precursor in palladium-catalyzed Suzuki and Sonogashira type cross-coupling reactions by replacing the carbon-chalcogen bond by new carbon-carbon bonds. Moreover, the 3-(phenylselanyl)prop-2-yn-1-yl benzoate has shown promising in vitro activity against glioblastoma cancer cells.

Stereodivergent Hydrosilylation, Hydrostannylation, and Hydrogermylation of α-Trifluoromethylated Alkynes and Their Synthetic Applications

Synthesis ◽  
2016 ◽  
Vol 48 (19) ◽  
pp. 3317-3330 ◽  
Author(s):  
Cédric Tresse ◽  
Stéphane Schweizer ◽  
Philippe Bisseret ◽  
Jacques Lalevée ◽  
Gwilherm Evano ◽  
...  
Keyword(s):  
Functional Group ◽  
Cross Coupling ◽  
Aryl Halides ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Palladium Catalyzed

Stereoselective hydrometalation reactions of aryl- and alkyl-substituted trifluoromethylated alkynes with triethylsilane, tributylstannane, and triphenylgermane have been investigated. (E)-α-CF3-Vinylsilanes, -stannanes, and -germanes were obtained under palladium-catalyzed conditions whereas the corresponding (Z)-α-CF3-vinylgermanes were obtained under radical conditions. These reactions proceed in good to excellent yields and possess a broad functional group tolerance. Applications of the (Z)- and (E)-α-CF3-vinylgermanes in palladium-catalyzed cross-coupling reactions with aryl halides having diverse electronic requirements were also investigated. The corresponding (Z)- and (E)-α-CF3-styrenes were obtained as single isomers, thus demonstrating the utility of these versatile synthons for the synthesis of stereodefined trifluoromethylated alkenes.

Ionic liquids in cross-coupling reactions: “liquid” solutions to a “solid” precipitation problem

2018 ◽  
Vol 54 (16) ◽  
pp. 2056-2059 ◽  
Author(s):  
Hemant Choudhary ◽  
Paula Berton ◽  
Gabriela Gurau ◽  
Allan S. Myerson ◽  
Robin D. Rogers
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Salt Precipitation ◽  
Solid Precipitation ◽  
Cross Coupling Reactions ◽  
Solid Salt ◽  
Liquid Solutions

To alleviate the problem of solid salt precipitation when using inorganic bases in cross-coupling reactions, basic anions were combined with the trihexyl(tetradecyl)phosphonium ([P66614]+) cation to ensure an ionic liquid byproduct.

Ionic Liquids: Valuable Solvents for Palladium Catalyzed C—P Cross-Coupling Reactions.

ChemInform ◽  
2007 ◽  
Vol 38 (5) ◽  
Author(s):  
H. Vallette ◽  
S. Pican ◽  
C. Boudou ◽  
J. Levillain ◽  
J. C. Plaquevent ◽  
...  
Keyword(s):  
Ionic Liquids ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Palladium Catalyzed
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