Cross-coupling reactions catalyzed by an N-heterocyclic carbene–Pd(ii) complex under aerobic and CuI-free conditions

RSC Advances ◽  
2014 ◽  
Vol 4 (57) ◽  
pp. 30447-30452 ◽  
Author(s):  
Hongfei Lu ◽  
Lin Wang ◽  
Feifei Yang ◽  
Runze Wu ◽  
Wei Shen
Keyword(s):  
Cross Coupling ◽  
Catalytic Reactions ◽  
Catalyst Loading ◽  
Coupling Reactions ◽  
Heck Reactions ◽  
Cross Coupling Reactions ◽  
Low Catalyst Loading

The catalytic reactions proceed with good yields with a low catalyst loading (1 mol%) under aerobic and CuI-free conditions for Sonogashira and Heck reactions.

scholarly journals Ferrocenylimine Palladium (II) Complexes: Synthesis, Characterization and Application in Mizoroki-Heck and Suzuki-Miyaura Cross-Coupling Reactions

Catalysts ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 755
Author(s):  
Asanda C. Matsheku ◽  
Richard Tia ◽  
Munaka C. Maumela ◽  
Banothile C. E. Makhubela
Keyword(s):  
Density Functional ◽  
Aryl Halide ◽  
Cross Coupling ◽  
Analytical Techniques ◽  
13C Nmr Spectroscopy ◽  
Catalyst Loading ◽  
Moderate Activity ◽  
Coupling Reactions ◽  
Heck Reactions ◽  
Cross Coupling Reactions

Carbon-carbon cross-coupling reactions are essential synthetic tools for synthesizing polymers, natural products, agrochemicals, and pharmaceuticals. Therefore, new catalysts that function with greater efficiency and functional group tolerance are being researched. We have prepared new ferrocenylimine monodentate N and P donor ligands and N^N and N^P bidentate chelating ligands (L1 to L4) employed in stabilizing palladium ions for application in Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions. The ferrocenylimine ligands were successfully synthesized by Schiff base condensation reactions of acetyl ferrocene with hydrazine monohydrate to afford ferrocenyl hydrazone (L1). Ligand L1 was further treated with aldehydes to give ferrocenyl(2-diphenylphosphino)imine (L3) and ferrocenyl(pyridyl)imine (L3), while phosphination of L1 with chlorodiphenylphosphine afforded L2. The ligands were used to prepare new palladium(II) complexes (C1 to C4) by complexation with [PdCl2(MeCN)2]. All the ligands and complexes were fully characterized using standard spectroscopic and analytical techniques, including 1H NMR and 13C NMR spectroscopy, FT-IR spectroscopy, mass spectrometry and elemental analysis. The complexes (C1 to C4) were tested for efficacies in catalyzing Mizoroki-Heck and Suzuki-Miyaura C-C cross-coupling reactions and proved to be suitable catalyst precursors. Ferrocenyl(2-diphenylphosphine)imino and ferrocenyl-methyl hydrazone palladium(II) complexes C2 and C3 showed the best activities at TONs of up to 201. The ferrocenyl palladium(II) (pre)catalysts demonstrated moderate activity in Mizoroki-Heck reactions involving substrates with substituents on the olefin and aryl halide (including 4-Cl, 4-CH3, -CO2Me and -CO2Et). Density Functional Theory was used to study the mechanism of the Mizoroki-Heck cross-coupling reactions and have led to confirmation of the widely accepted catalytic cycle. Catalyst precursors (C1 to C4) also displayed good activity and selectivity in Suzuki-Miyaura cross-coupling reactions, at 0.5 mol% catalyst loading, with good tolerance to functional groups present on the aryl halide and boronic acid substrates (such as 4-Cl, 4-CHO, 4-COOH, 3-NO2, 3,5-dimethoxy and 4-CH3).

scholarly journals A Self-Assembling NHC-Pd-Loaded Calixarene as a Potent Catalyst for the Suzuki-Miyaura Cross-Coupling Reaction in Water

Molecules ◽  
2020 ◽  
Vol 25 (6) ◽  
pp. 1459
Author(s):  
Arnaud Peramo ◽  
Ibrahim Abdellah ◽  
Shannon Pecnard ◽  
Julie Mougin ◽  
Cyril Martini ◽  
...  
Keyword(s):  
Coupling Reaction ◽  
Cross Coupling ◽  
Palladium Complexes ◽  
Water Soluble ◽  
Catalyst Loading ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Self Assembling ◽  
Cross Coupling Reaction ◽  
Low Catalyst Loading

Nanoformulated calix[8]arenes functionalized with N-heterocyclic carbene (NHC)-palladium complexes were found to be efficient nano-reactors for Suzuki-Miyaura cross-coupling reactions of water soluble iodo- and bromoaryl compounds with cyclic triol arylborates at low temperature in water without any organic co-solvent. Combined with an improved one-step synthesis of triol arylborates from boronic acid, this remarkably efficient new tool provided a variety of 4′-arylated phenylalanines and tyrosines in good yields at low catalyst loading with a wide functional group tolerance.

scholarly journals Dimethylisosorbide (DMI) as a Bio-Derived Solvent for Pd-Catalyzed Cross-Coupling Reactions

Synlett ◽  
2018 ◽  
Vol 29 (17) ◽  
pp. 2293-2297 ◽  
Author(s):  
Allan Watson ◽  
Kirsty Wilson ◽  
Jane Murray ◽  
Helen Sneddon ◽  
Craig Jamieson
Keyword(s):  
Chemical Industry ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Heck Reactions ◽  
Bond Forming ◽  
Cross Coupling Reactions ◽  
Bond Forming Reactions ◽  
Palladium Catalyzed ◽  
Catalyzed Reactions

Palladium-catalyzed bond-forming reactions, such as the ­Suzuki–Miyaura and Mizoroki–Heck reactions, are some of the most broadly utilized reactions within the chemical industry. These reactions frequently employ hazardous solvents; however, to adhere to increasing sustainability pressures and restrictions regarding the use of such solvents, alternatives are highly sought after. Here we demonstrate the utility of dimethyl isosorbide (DMI) as a bio-derived solvent in several benchmark Pd-catalyzed reactions: Suzuki–Miyaura (13 examples, 62–100% yield), Mizoroki–Heck (13 examples, 47–91% yield), and Sonogashira (12 examples, 65–98% yield).

Suzuki–Miyaura cross-coupling coupling reactions with low catalyst loading: a green and sustainable protocol in pure water

2011 ◽  
Vol 40 (13) ◽  
pp. 3116 ◽  
Author(s):  
Aziz Fihri ◽  
Denis Luart ◽  
Christophe Len ◽  
Abderrahim Solhy ◽  
Carole Chevrin ◽  
...  
Keyword(s):  
Pure Water ◽  
Cross Coupling ◽  
Catalyst Loading ◽  
Coupling Reactions ◽  
Low Catalyst Loading

scholarly journals A new hierarchically porous Pd@HSQ monolithic catalyst for Mizoroki–Heck cross-coupling reactions

2014 ◽  
Vol 38 (3) ◽  
pp. 1144-1149 ◽  
Author(s):  
Nirmalya Moitra ◽  
Ayumi Matsushima ◽  
Toshiyuki Kamei ◽  
Kazuyoshi Kanamori ◽  
Yumi H. Ikuhara ◽  
...  
Keyword(s):  
Palladium Nanoparticles ◽  
Cross Coupling ◽  
Reusable Catalyst ◽  
Coupling Reactions ◽  
Hydrogen Silsesquioxane ◽  
Heck Reactions ◽  
Hierarchically Porous ◽  
Monolithic Catalyst ◽  
Cross Coupling Reactions

Palladium nanoparticles are embedded in hierarchically porous hydrogen silsesquioxane monoliths by on-site reduction to prepare a reusable catalyst for Mizoroki–Heck reactions.

scholarly journals New trends in the cross-coupling and other catalytic reactions

2017 ◽  
Vol 89 (10) ◽  
pp. 1413-1428 ◽  
Author(s):  
Irina P. Beletskaya ◽  
Alexei D. Averin
Keyword(s):  
Lewis Acids ◽  
Bond Formation ◽  
Cross Coupling ◽  
Pd Nanoparticles ◽  
Catalytic Reactions ◽  
Coupling Reactions ◽  
Ch Activation ◽  
Cross Coupling Reactions ◽  
Palladium Catalyzed ◽  
Catalyzed Reactions

AbstractA mini-review covers the latest achievements in the field of metal-mediated cross-coupling reactions among which are palladium-catalyzed Heck, Suzuki, cyanation and amination reactions. The aspects of the application of Pd nanoparticles (PdNPs) are discussed. The possibilities of the applications of Cu(I)-catalyzed reactions are described. Special emphasis is made on the synthesis of polymacrocyclic compounds like porphyrin dyads and triads, polyazacryptands bearing fluorophore groups using catalytic methods. The application of Pd-catalyzed CH-activation reactions for porphyrin modifications is described, the use of Lewis acids catalysis and organocatalysis for enantioselective C–C bond formation is considered with the emphasis on the application of immobilized organocatalyst.

Aryl-Decarboxylation Reactions Catalyzed by Palladium: Scope and Mechanism

Synthesis ◽  
2019 ◽  
Vol 52 (03) ◽  
pp. 365-377 ◽  
Author(s):  
Ryan A. Daley ◽  
Joseph J. Topczewski
Keyword(s):  
Carboxylic Acids ◽  
Boronic Acid ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Heck Reactions ◽  
Cross Coupling Reactions ◽  
Related Family ◽  
Organometallic Precursor ◽  
Palladium Catalyzed ◽  
Catalyzed Reactions

Palladium-catalyzed cross-couplings and related reactions have enabled many transformations essential to the synthesis of pharmaceuticals, agrochemicals, and organic materials. A related family of reactions that have received less attention are decarboxylative functionalization reactions. These reactions replace the preformed organometallic precursor (e.g., boronic acid or organostannane) with inexpensive and readily available carboxylic acids for many palladium-catalyzed reactions. This review focuses on catalyzed reactions where the elementary decarboxylation step is thought to occur at a palladium center. This review does not include decarboxylative reactions where decarboxylation is thought to be facilitated by a second metal (copper or silver) and is specifically limited to (hetero)arenecarboxylic acids. This review includes a discussion of oxidative Heck reactions, protodecarboxylation reactions, and cross-coupling reactions among others.1 Introduction2 Oxidative Heck Reactions3 Protodecarboxylation Reactions4 Cross-Coupling Reactions5 Other Reactions6 Conclusion

The Role of PEG on Pd- and Cu-Catalyzed Cross-Coupling Reactions

Synthesis ◽  
2017 ◽  
Vol 49 (11) ◽  
pp. 2337-2350 ◽  
Author(s):  
Marina Pires ◽  
Sara Purificação ◽  
A. Santos ◽  
M. Marques
Keyword(s):  
Phase Transfer ◽  
Cross Coupling ◽  
Polymer Support ◽  
Coupling Reactions ◽  
Heck Reactions ◽  
Cross Coupling Reactions ◽  
Direct Formation ◽  
Metal Catalyzed ◽  
Sonogashira Reactions

Carbon–carbon and carbon–heteroatom coupling reactions are among the most important transformations in organic synthesis as they enable complex structures to be formed from readily available compounds under different routes and conditions. Several metal-catalyzed cross-coupling reactions have been developed creating many efficient methods accessible for the direct formation of new bonds between differently hybridized carbon atoms.During the last decade, much effort has been devoted towards improvement of the sustainability of these reactions, such as catalyst recovery and atom efficiency. Polyethylene glycol (PEG) can be used as a medium, as solid-liquid phase transfer catalyst, or even as a polymer support. PEG has been investigated in a wide variety of cross-coupling reactions either as an alternative solvent to the common organic solvents or as a support for catalyst, substrate, and ligand. In this review we will summarize the different roles of PEG in palladium- and copper-catalyzed cross-coupling reactions, with the focus on Heck, Suzuki–Miyaura, Sonogashira, Buchwald–Hartwig, Stille, Fukuyama, and homocoupling reactions. We will highlight the role of PEG, the preparation of PEGylated catalysts and substrates, and the importance for the reaction outcome and applicability.1 Introduction2 PEG in Heck Reactions3 PEG in Homocoupling Reactions4 PEG in Suzuki–Miyaura Reactions5 PEG in Sonogashira Reactions6 PEG in Buchwald–Hartwig Reactions7 PEG in Stille Reactions8 PEG in Fukuyama Reactions9 PEG in Miscellaneous Cross-Coupling Routes10 Conclusions

scholarly journals Thiosemicarbazone Complexes of Transition Metals as Catalysts for Cross-Coupling Reactions

Catalysts ◽  
2020 ◽  
Vol 10 (10) ◽  
pp. 1107
Author(s):  
Ioannis D. Kostas ◽  
Barry R. Steele
Keyword(s):  
Transition Metal Complexes ◽  
Homogeneous Catalysis ◽  
Cross Coupling ◽  
Catalytic Reactions ◽  
Coupling Reactions ◽  
Future Developments ◽  
Cross Coupling Reactions ◽  
Thiosemicarbazone Complexes ◽  
Complexes Of Transition Metals ◽  
Long Time

Catalysis of cross-coupling reactions under phosphane-free conditions represents an important ongoing challenge. Although transition metal complexes based on the thiosemicarbazone unit have been known for a very long time, their use in homogeneous catalysis has been studied only relatively recently. In particular, reports of cross-coupling catalytic reactions with such complexes have appeared only in the last 15 years. This review provides a survey of the research in this area and a discussion of the prospects for future developments.

Sign in / Sign up

Export Citation Format

Share Document