Mizoroki Heck Cross-coupling Reactions Research Articles

PdII Immobilized on Ferromagnetic Multi-Walled Carbon Nanotubes Functionalized by Aminated 2-Chloroethylphosphonic Acid with S-Methylisothiourea (FMMWCNTs@CPA@SMTU@PdII NPs) Applied as a Highly Efficient and Recyclable Nanostructured Catalyst for Suzuki–Miyaura and Mizoroki–Heck Cross-Coupling Reactions in Solvent-Free Conditions

The new ferromagnetic nanostructured FMMWCNTs@CPA@SMTU@PdII NPs (IV) as an eco-friendly heterogeneous nanocatalyst with a particle size of ~20–30nm reported earlier by our group has been found to be very effective for Suzuki–Miyaura and Mizoroki–Heck cross-coupling reactions at ambient temperature. The procedure has been applied for a wide range of aryl halides, arylboronic acids, and alkenes. The magnetic separation by an external magnetic field, mild reaction conditions, and catalyst reusability up to four times without significant decrease in catalytic activity (reduced catalytic activity from 11 to 18% in the fifth, sixth, and seventh cycles) made the present method sustainable and economically viable for C–C cross-coupling reactions.

Synthesis of new Pro-PYE ligands as co-catalysts toward Pd-catalyzed Heck-Mizoroki cross coupling reactions.

The present research work describes the synthesis of five new ligands containing pyridinium amine, [H2L1][OTf]2–[H2L5][I]2 from two new precursors, [P3Et][I] and [P2Me][CF3SO3]. The structure elucidations of the compounds were confirmed by multinuclear NMR (1H, 13C), FT-IR and by single crystal XRD techniques. Theoretical DFT studies were carried out to get better insight into the electronic levels and structural features of all the molecules. These synthesized new Pro-PYE ligands [H2L1][OTf]2–[H2L5][I]2 were found to be significantly active as co-catalysts for Pd(CH3CO2)2 toward Heck–Mizoroki coupling reactions with wide substrate scope in the order of [H2L1][OTf]2 ≫ [H2L2][OTf]2 > [H2L3][OTf]2 > [H2L4][OTf]2 > [H2L5][I]2.

Architectured Fe3Pd2(OH)2[picolinic acid]8(H2O)4 Hybrid Nanorods: A Remarkably Reusable and Robust Heterogeneous Catalyst for Suzuki–Miyaura and Mizoroki–Heck Cross-Coupling Reactions

Pd/Fe-catalyzed Mizoroki–Heck and Suzuki–Miyaura cross-coupling reactions are among the important C–C bond-forming reactions. In the present work, new approaches were evaluated systematically for preparing heterogeneous Pd-based catalysts with high activities. For the first time architectured organic–inorganic Fe3Pd2(OH)2[PA]8(H2O)4 hybrid nanorods were reported. They were fabricated by solvothermal reaction of K2PdCl4 with picolinic acid (PA) (chelating agent) in the presence of Fe(NO3)2 and an excess amount of base. This reaction produces isostructural coordination complex ligands containing palladium coordinate to Fe–OH chains. As-prepared Fe3Pd2(OH)2[PA]8(H2O)4 hybrid nanorods are a promising new catalyst candidate for Suzuki–Miyaura and Mizoroki–Heck cross-coupling reactions. Usually, the catalytic activity with Pd-based catalysts was characterized by reaction times, catalyst usage, and reusability of the catalyst. The Fe3Pd2(OH)2[PA]8(H2O)4 catalyst demonstrates excellent catalytic activity for Suzu...

Controlled synthesis of modified polyacrylamide grafted nano-sized silica supported Pd nanoparticles via RAFT polymerization through “grafting to” approach: application to the Heck reaction

Polyacrylamide grafted onto silica nanoparticles (nano-SiO2-g-PAAm) was prepared through “grafting to” approach via controlled reversible addition-fragmentation chain transfer (RAFT) polymerization system with defined molecular weight and graft density. Modification of the nano-SiO2-g-PAAm with ethanolamine and subsequent reaction with chlorodiphenylphosphine (ClPPh2) was produced polymer-grafted silica with phosphinite functionality which was converted to Pd catalyst through the reaction with Pd(OAc)2. The catalyst was characterized using ICP, FT-IR, TGA, SEM, and DLS methods properly. Dispersion of palladium nanoparticles (PdNPs) in the polymer matrix (10–15-nm range) and existence of Pd in zero oxidation state was verified by TEM and XRD techniques. The catalyst demonstrated activity in the Mizoroki-Heck cross-coupling reaction of varied iodoarenes including electron poor, electron rich, and ortho substituted and heterocycles with olefins efficiently. Reusing of the Pd catalyst was performed at least five times in repeating runs without considerable palladium leaching and change of the catalyst function and structure.

Pd salen complex@CPGO as a convenient, effective heterogeneous catalyst for Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions

A Pd(II) Schiff base complex supported on graphene oxide nanosheets (Pd(II) salen@CPGO) has been synthesized and characterized by FT-IR, ICP-AES, XRD, SEM/EDX and TEM. The synthesized nanocatalyst has been found to be an efficient heterogeneous catalyst for Suzuki–Miyaura and Heck–Mizoroki coupling reactions. Pd(II) salen@CPGO could be separated and recovered easily from the reaction mixture and recycled several times without a discernible decrease in its catalytic activity. The construction of a solid sheet-supported Pd catalyst would be expected to be a promising system to perform heterogeneous catalytic reactions.

Pd(OAc)2 immobilized on imine-functionalized microporous covalent triazine polymer as efficient heterogeneous catalyst for Mizoroki–Heck cross-coupling reaction

A template consisting of Pd(OAc)2 immobilized on imine-functionalized microporous covalent triazine polymer network (Pd/TATAE) was synthesized and found to be an efficient and recyclable heterogeneous solid catalyst for Mizoroki–Heck C–C coupling of styrene with substituted aryl halides under mild reaction conditions and without addition of any ligand or additives. Furthermore, Pd/TATAE could be recycled for nine consecutive cycles with minor loss of catalytic activity. Finally, the Pd/TATAE catalyst showed good catalytic activity with excellent yield of 96 % and high turnover number of 3349.

Palladium-Loaded Cucurbit[7]uril-Modified Iron Oxide Nanoparticles for C-C Cross-Coupling Reactions.

Cucurbit[7]uril modified iron oxide nanoparticles (CB[7]NPs) were loaded with palladium to form nano-catalysts (Pd@CB[7]NPs) that, with microwave heating, catalysed Suzuki-Miyaura, Sonogashira, and Mizoroki-Heck cross-coupling reactions. Reactions were run in environmentally benign 1:1 ethanol/water solvent under convenient aerobic conditions. In a preliminary screening, conversions and yields were uniformly high with turn over frequencies (TOF) ranging from 64 to 7360 h-1 . The nano-catalysts could be recovered with a magnet and reused several times (6 times for Suzuki-Miayura reaction) without loss of activity.

Synthesis of a novel ZnO nanoplates supported hydrazone-based palladacycle as an effective and recyclable heterogeneous catalyst for the Mizoroki-Heck cross-coupling reaction

Abstract A new hydrazone-based palladacycle complex was successfully prepared onto ZnO nanoplates support and was fully identified by using a variety of methods such as energy dispersive X-ray spectroscopy (EDX), Brunauer-Emmett-Teller analysis (BET), inductively coupled plasma technique (ICP), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The morphology of nanoplates support has been also confirmed by scanning electron microscopy (SEM) and powder X-ray diffraction (XRD). Furthermore, it was shown that ZnO nanoplates supported hydrazone-based palladacycle can act as a highly efficient heterogeneous catalyst for the Mizoroki-Heck cross-coupling reaction with excellent yields. The reaction was successfully carried out between aryl iodides, bromides or even aryl chlorides with a variety of olefins. Additionally, it is possible to isolate the catalyst from the reaction mixture and reused for eight sequential cycles without remarkable decrease in catalytic activity.

Merrifield’s Resin-Supported Palladium–Bis(oxazoline) Complex-Catalyzed Cross-Coupling Reactions of Aryl Bromides and Aryl Chlorides

The catalytic activity and the recycling ability of palladium–bis(oxazoline) (Pd–BOX-M) complex supported on Merrifield’s resin have been investigated in Suzuki–Miyaura and Mizoroki–Heck cross-coupling reactions of aryl bromides and aryl chlorides. The supported palladium–bis(oxazoline) catalyst demonstrated exceptional catalytic activity and excellent recycling ability. The characterization of the recycled palladium catalyst reveals no significant change in its structure, oxidation state and the amount of loaded palladium. This confirms the excellent stability of the palladium-supported catalyst.

Synthesis of (Ph3P)2PdX2 complexes and their catalytic activity for Heck reaction involving aryl halide and acrylate

Two palladium complexes, (Ph3P)2PdBr2 and (Ph3P)2PdI2, were synthesized by a new method and their structures were confirmed by NMR, elemental analysis and X-ray crystallography. The catalytic activity of the two palladium complexes was evaluated in Mizoroki-Heck cross-coupling reaction of aryl halide with acrylate, the results show that they all have high catalytic activity to many different substrates.

Catalysis of Cross-Coupling and Homocoupling Reactions of Aryl Halides Utilizing Ni(0), Ni(I), and Ni(II) Precursors; Ni(0) Compounds as the Probable Catalytic Species but Ni(I) Compounds as Intermediates and Products

Both Ni(0) and Ni(I) compounds are believed to exhibit cross-coupling catalytic properties under various conditions, and the compounds Ni(PPh3)4 and NiCl(PPh3)3 are compared as catalysts for representative Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions. The Ni(0) compound exhibits catalytic activities, for cross-coupling of chloro and bromoanisole with phenylboronic acid and of bromobenzene with styrene, yielding results which are comparable with those of many palladium-based catalysts, but our findings with NiCl(PPh3)3 are at this point unclear. It seems to convert to catalytically active Ni(0) species under Suzuki–Miyaura reaction conditions and is ineffective for Heck–Mizoroki cross-coupling. The paramagnetic Ni(I) compounds NiX(PPh3)3 (X = Cl, Br, I) are characterized for the first time by 1H NMR spectroscopy and are found to exhibit broad meta and para resonances at δ 9–11 and 3–4, respectively, and very broad ortho resonances at δ 4−6; these resonances are very useful for detecting Ni(I) ...

Thiophene Methanimine–Palladium Schiff Base Complex Anchored on Magnetic Nanoparticles: A Novel, Highly Efficient and Recoverable Nanocatalyst for Cross-Coupling Reactions in Mild and Aqueous Media

In this study, a novel thiophene methanimine–palladium Schiff base complex anchored on decorated γ-Fe2O3 with 2-aminoethyl dihydrogen phosphate (γ-Fe2O3/AEPH2-TC-Pd) was synthesized as a new magnetically separable nanocatalyst. Characterization of the new designed nanocatalyst was performed successfully using different techniques such as FT-IR, XRD, XPS, TEM, TGA, VSM, ICP and elemental analysis. This nanocatalyst presented a superb catalytic activity for Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions. The most important features of the prepared catalytic system which makes the current protocol more beneficial from both industrial and environmental viewpoints are its ease of recovery and reusability up to nine cycles without appreciable loss of the catalytic performance, as well as accomplishing the reactions under mild conditions in aqueous media which is a great challenge in some cross-coupling reactions.

Pd/Indanone-Based Ligands: An Efficient Catalyst System for Ullmann­-Type, Suzuki–Miyaura, and Mizoroki–Heck Cross-Coupling Reactions with Aryl Tosylates and Aryl Halides

2-Hydroxyindan-1-ones have been efficiently synthesized and successfully applied as ligands in Pd-catalyzed Ullmann type, Suzuki–Miyaura, and Mizoroki–Heck cross-coupling reactions with aryl tosylates and aryl halides. The ligands are air- and moisture-stable and have shown high catalytic activity with Pd(OAc)2 in these cross-coupling reactions. The system tolerates a variety of functional groups in the product and can be re-used at least three times with maximum efficiency.

A strategic approach to [6,6]-bicyclic lactones: application towards the CD fragment of DHβE.

We report an effective synthetic protocol to access [6,6]-bicyclic lactone moieties through a regio- and stereoselective intramolecular Mizoroki–Heck cross-coupling reaction followed by a 6π-electrocyclization. This method enabled the first synthesis of the elusive CD fragment of the Erythrina alkaloid DHβE. Preliminary pharmacological evaluations support the notion that the key pharmacophores of DHβE are located in the A and B rings.

Mizoroki–Heck Cross-Coupling Reaction of Haloarenes Mediated by a Well-Controlled Modified Polyacrylamide Brush Grafted Silica/Pd Nanoparticle System

Abstract Modified polyacrylamide brushes including phosphinite functionality grafted onto silica supported Pd nanoparticles were synthesized via RAFT polymerization technique in a controlled manner with elucidated graft density and chain length. Proper activity of the catalyst was indicated in the Mizoroki–Heck coupling reaction of various haloarenes with olefins. Different aryl iodides with electron rich and electron deficient substituent and also ortho and heterocyclic substrate showed good reactivity to generate the corresponding coupled products in good to excellent yields using low Pd loading. The turnover number (TON) for this catalyst can be reduced up to 9.5 × 103. Simple filtration, appropriate reusability and negligible palladium leaching of this catalyst are among other advantages.

A convenient, efficient and reusable N-heterocyclic carbene-palladium(ii) based catalyst supported on magnetite for Suzuki–Miyaura and Mizoroki–Heck cross-coupling reactions

In the present work, a new magnetic nanoparticle supported N-heterocyclic carbene-palladium(ii) (NO2-NHC-Pd@Fe3O4) nanomagnetic catalyst was synthesized by a facile multistep synthesis under aerobic conditions.

Fe3O4@Boehmite-NH2-CoIINPs: an inexpensive and highly efficient heterogeneous magnetic nanocatalyst for the Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions

CoIIimmobilized on aminated Fe3O4@Boehmite nanoparticles as a heterogeneous magnetic catalyst for cross-coupling reactions was investigated.

Efficient nickel(ii) naringenin-oxime complex catalyzed Mizoroki–Heck cross-coupling reaction in the presence of hydrazine hydrate

A novel nickel(ii) naringenin-oxime complex was designed, synthesized and characterized.

Aminophosphine Palladium(0) Complex Supported on ZrO2 Nanoparticles (ZrO2@AEPH2-PPh2-Pd(0)) as an Efficient Heterogeneous Catalyst for Suzuki–Miyaura and Heck–Mizoroki Reactions in Green Media

A new aminophosphine palladium(0) complex supported on ZrO2 nanoparticles (ZrO2@AEPH2-PPh2-Pd(0)) was successfully synthesized and characterized using FT-IR, XRD, XPS, SEM, TEM, EDS, TGA and ICP techniques. Characterization results revealed that the synthesized catalyst had tetragonal and monoclinic structure with spherical morphology. The prepared nanocatalyst was showed excellent reactivity in the Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions. Moreover, this nanocatalyst can be easily recovered and reused for at least six cycles without deterioration in catalytic activity.

Phenylenevinylene oligomers by Mizoroki-Heck cross coupling reaction. Structural and optoelectronic characterization

In order to study the effect of the molecular structure on the optical properties of totally trans-trans phenylenevinylene oligomers (OPVs), sixteen 1,4-distyrylbenzene derivatives (1a-i and 2a-g) functionalized with different electron-donating (ED) and electron-withdrawing (EW) groups were synthesized by the Mizoroki-Heck cross coupling reaction in moderate to good yields (40–95%). The implemented methodology, with a small modification previously reported by our group, allows obtaining the desired vinyl configuration as well as one novel OPV compound (1h). After structural characterization by several techniques (e.g. FTIR, 1H, 13C and Solid-State NMR), particular emphasis was placed upon the investigation of their optical properties by UV–vis and fluorescence spectroscopies. The results showed that, with only one exception, the ED and EW groups at the ends of OPV systems lead to a bathochromic shift. This effect is intensified with the introduction of methoxy groups on the central ring. Consistent with these, the HOMO-LUMO gaps (ΔE) decreases as the strength of ED and EW substituents increases. The ED and EW substituents also lead to a decrease in the Φf values. This contribution in the area of organic electronics can be used as a reference to better select the most appropriate technological application for each OPV and this can be extrapolated to their respective structurally analogous segmented polymer.