292625-97-9Relevant articles and documents
A ferrocene based palladacyclic precatalyst for the Suzuki cross-coupling of aryl chlorides
Roca, Francesc X.,Richards, Christopher J.
, p. 3002 - 3003 (2003)
Addition of palladium acetate to 2-(dicyclohexylphosphino)-phenylferrocene gave palladacycle 16 that is a very effective precatalyst for the Suzuki cross-coupling of aryl chlorides at room temperature (1 mol% 16) or 60°C (≥ 0.01 mol% 16).
Alkali-metal-mediated manganation(II) of functionalized arenes and applications of ortho-manganated products in Pd-catalyzed cross-coupling reactions with iodobenzene
Blair, Victoria L.,Clegg, William,Conway, Ben,Hevia, Eva,Kennedy, Alan,Klett, Jan,Mulvey, Robert E.,Russo, Luca
, p. 65 - 72 (2008)
Extending the recently introduced concept of "alkali-metal-mediated manganation" to functionalised arenes, the heteroleptic sodium manganate reagent [(tmeda)Na(tmp)(R)Mn(tmp)] (1; TMEDA = N,N,N′,N′-tetra- methylethylenediamine, TMP = 2,2.6,6-tetramethylpiperidide, R = CH 2SiMe3) has been treated with anisole or N,N-diisopropylbenzamide in a 1:1 stoichiometry in hexane. These reactions afforded the crystalline products [(tmeda)Na(tmp)(o-C6H 4OMe)Mn-(tmp)] (2) and [(tmeda)Na(tmp){o(C(O)N(iPr)2C 6H4)Mn(CH2SiMe3)] (3), respectively, as determined from X-ray crystallography studies. On the basis of these products, it can be surmised that reagent 1 has acted, at least partially and ultimately, as an alkyl base in the first reaction liberating the silane Me 4Si, but as an amido base in the second reaction liberating the amine TMPH. Both of these paramagnetic products 2 and 3 have contacted ion-pair structures, the key features of which are six-atom, five-element (NaNMnCCO) and seven-atom, five-element (NaNMnCCCO) rings, respectively. Manganates 2 and 3 were successfully cross-coupled with iodobenzene under [PdCl2(dppf)] (dppf = 1,1′-bis(diphenylphosphino)ferrocene) catalysis to generate unsymmetrical biaryl compounds in yields of 98.0 and 66.2%, respectively. Emphasizing the importance of alkali-metal mediation in these manganation reactions, the bisalkyl Mn reagent on its own fails to metalate the said benzamide, but instead produces the monomeric, donoracceptor complex [Mn(R) 2{(iPr)2-NC(Ph)(=O)}2] (5), which has also been crystallographically characterised. During one attempt to repeat the synthesis of 2, the butoxide-contaminated complex [{(tmeda)Na(R)(OBu)(o-C 6H4OMe)Mn}2] (6) was obtained. In contrast to 2 and 3, due to reduced steric constraints, this complex adopts a dimeric arrangement in the crystal, the centrepiece of which is a twelve atom (NaOCCMnC)2 ring.
Encapsulation of palladium chloride using 2-formylbenzoic acid supported by Fe3O4 nanoparticles modified with SiO2 and propylamine, its characterization and its application for Suzuki coupling reaction
Mostafavi, Hamid,Islami, Mohammad Reza,Momeni Tikdari, Ahmad
, (2018)
A magnetically separable heterogeneous nanocatalyst, Fe3O4@SiO2(CH2)3N―CH―Ar@Pd(0), was simply prepared and characterized using various techniques. The catalytic activity of this nanocatalyst was evaluated via the Suzuki–Miyaura cross-coupling reaction of aryl halides with phenylboronic acid under various experimental conditions such as kind of base, solvent and temperature. This nanocatalyst is completely magnetically recoverable because of the superparamagnetic behaviour of Fe and can be reused with sustained selectivity and activity.
Noncovalent Immobilization of Palladium Complex onto Reduced Graphene Oxide: A Highly Efficient and Recyclable Catalyst for Suzuki Reaction
Qian, Yingjie,Jung, Sang-Yung,Jin, Myung-Jong
, p. 477 - 478 (2019)
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Synthesis of Pd immobilized on functionalized hexagonal mesoporous silica (HMS–CPTMS–Cy–Pd) for coupling Suzuki–Miyaura and Stille reactions
Gholamian, Fatemeh,Hajjami, Maryam
, p. 649 - 658 (2019)
In this paper, Pd–cytosine complex immobilized on functionalized hexagonal mesoporous silica (HMS–CPTMS–Cy–Pd) as a novel mesoporous catalyst with high activity for the Stille and Suzuki coupling reactions was successfully fabricated. All products were obtained in good to excellent yields at low time reaction. The prepared catalyst has been characterized using various techniques such as FT-IR, XRD, BET, SEM, EDX-MAP, TGA and ICP. Recovery test confirm that the synthesized catalyst can be able to reuse for several times.
Starch assisted palladium(0) nanoparticles as in situ generated catalysts for room temperature Suzuki-Miyaura reactions in water
Dewan, Anindita,Bharali, Pankaj,Bora, Utpal,Thakur, Ashim Jyoti
, p. 11758 - 11761 (2016)
A simple and efficient methodology for the in situ generation of Pd-nanoparticles in the presence of starch and NaOH at room temperature has been developed. It has been observed that starch played a dual role in controlling the reduction rate of metal ions and the aggregation process of metal atoms in solution. The in situ generated Pd-nanoparticles show excellent catalytic activity in the Suzuki-Miyaura cross coupling reaction of electronically diversified arylbromides and arylboronic acids in pure water at room temperature with low catalyst loading.
Monodisperse noble metal nanoparticles stabilized in SBA-15: Synthesis, characterization and application in microwave-assisted Suzuki-Miyaura coupling reaction
Zheng, Zhaoliang,Li, Hongfang,Liu, Tianfu,Cao, Rong
, p. 268 - 274 (2010)
A series of Pd and Pd/Au alloy nanoparticles (NPs) with narrow size distribution were encapsulated or stabilized by G4-poly (amido-amine) (G4-PAMAM, G represents the generation) planted in SBA-15. Monodisperse NPs are uniformly distributed in channels of SBA-15 as observed by TEM images. HRTEM, ICP and EDS results confirm the alloy structure of bimetallic NPs. A combination of N2 adsorption-desorption analysis, ICP and GC was used to optimize the best amount of metal precursors to form catalysts. The as-prepared catalyst manifests outstanding activity and recyclability in microwave-assisted Suzuki-Miyaura coupling reaction when compared with commercial Pd/C. Meanwhile, Pd/Au alloy NPs exhibit higher activity than monometallic ones in catalyzing the coupling between aryl bromide/aryl chloride and arylboronic acid. The mechanism of the improvement of catalytic performance is discussed.
Facile and efficient Suzuki-Miyaura coupling reaction of aryl halides catalyzed by Pd2(dba)3 in ionic liquid/supercritical carbon dioxide biphasic system
Wang, Hong Bo,Hu, Yu-Lin,Li, De-Jiang
, p. 429 - 433 (2016)
A general and efficient catalytic system for Pd2(dba)3-catalyzed ligand-free Suzuki cross-coupling reactions was developed. The cross-couplings of a wide range of aryl halides with various arylboronic acids were feasible under mild conditions in environmental friendly [hmim]NTf2/supercritical CO2 biphasic system employing K2CO3 as a base, which provided in good to high yields to the corresponding products. The catalytic system could be recycled and reused without significant loss of catalytic activity. Additionally, a possible mechanism of the Suzuki cross-coupling reaction is depicted in this paper.
Anchoring palladium acetate onto imine-functionalized silica gel through coordinative attachment: An effective recyclable catalyst for the Suzuki-Miyaura reaction in aqueous-isopropanol
Sarmah, Chandan,Sahu, Debojeet,Das, Pankaj
, p. 197 - 203 (2012)
Silica supported palladium catalyst, Pd@imine-SiO2, was prepared by immobilizing Pd(OAc)2 onto silica gel through coordination of imine, generated via Schiff-base condensation between 3- aminopropyltriethoxysilane (APTES) functionalized silica gel and acetamide. The catalyst was characterized by FTIR, BET surface area measurements, XRD, SEM-EDX and ICP-AES. The imine-based catalyst, exhibited excellent activity for the Suzuki-Miyaura cross-coupling reactions of aryl halides with arylboronic acids in iPrOH/H2O (1:1) under mild conditions (T = 60 °C, air, 0.08 mol% of palladium). Interestingly, under the same experimental conditions, for the reaction between p-bromoanisole and phenylboronic acid the imine-based catalyst, Pd@imine-SiO2, exhibited comparable result with that of homogeneous Pd(OAc)2 and much higher activity than amine-based catalyst, Pd@APTES-SiO2. Furthermore, the imine-based catalyst could be recovered by simple filtration and reused several times without significant loss of activity.
Synthesis, structure and reactivity of NHC-nickel complexes containing carbonato ligands
Guo, Jin,Lv, Lanlan,Wang, Xiaojun,Cao, Changsheng,Pang, Guangsheng,Shi, Yanhui
, p. 74 - 78 (2013)
Reactions of different alkane-bridged (n = 1-3) di-NHC precursors, bisimidazolium chlorides with the NiCl2 in presents of K 2CO3 in acetonitrile give the corresponding 16-electron binuclear complexes of the type Ni(di-NHC)(μ-O)2CO in moderate yield. The molecular structures of 1-3 have been determined by X-ray crystallography, which revealed a cis-chelating di-NHC on a slightly distorted square-planar nickel center with κ2-cabonato ligand. The influence of the different di-NHC ligands on the structure and reactivity of the complexes has been studied. The catalytic properties of the complexes were investigated in the Kumada reaction for cross-coupling of phenylmagnesium bromide with a variety of aryl halides. The complex 3 which has the longest linker between two NHCs shows the best catalytic activity in these reactions.
Fluoride-Free Hiyama Coupling Reaction Catalyzed by Linear Polystyrene-Stabilized PdO Nanoparticles in Water: Specific Reactivity of PdO Nanoparticles over Pd Nanoparticles
Ohtaka, Atsushi,Kotera, Takamasa,Sakon, Akira,Ueda, Kouhei,Hamasaka, Go,Uozumi, Yasuhiro,Shinagawa, Tsutomu,Shimomura, Osamu,Nomura, Ry?ki
, p. 1202 - 1206 (2016)
Linear polystyrene-stabilized PdO nanoparticles (PS-PdONPs) exhibited high catalytic activity for fluoride-free Hiyama coupling reaction of aryltrimethoxysilanes with a variety of bromoarenes under air in water. In contrast, no desired coupling product was obtained from the Hiyama coupling reaction using linear polystyrene-stabilized Pd nanoparticles (PS-PdNPs) as a catalyst. The different reactivities of PdONPs and PdNPs will be discussed.
Pyridine-based hypercrosslinked polymers as support materials for palladium photocatalysts and their application in Suzuki-Miyaura coupling reactions
Zhang, Yan,Zhang, Le,Zhang, Xiaoli,Yang, Didi,Du, Cheng,Wan, Liu,Au, Chaktong,Chen, Jian,Xie, Mingjiang
, p. 15202 - 15208 (2020)
A series of hypercrosslinked polymers (P1 to P8) was synthesized from pyridine and conjugated monomers to support palladium for photocatalytic Suzuki-Miyaura coupling reactions. The results of SEM, TEM and XRD analyses reveal that the supports possess a loose porous amorphous lamellar structure, and the TGA test shows that they are thermally stable. Among the prepared photocatalysts, the one using P6 as a support performed the best, displaying excellent photocatalytic and recycling performance under the irradiation of blue light at 30 °C.
Unparalleled rates for the activation of aryl chlorides and bromides: Coupling with amines and boronic acids in minutes at room temperature
Stambuli, James P.,Kuwano, Ryoichi,Hartwig, John F.
, p. 4746 - 4748 (2002)
Exceptionally fast oxidative addition of an aryl chloride (or a deactivated aryl bromide) to the active Pd0 center, which is ligated by sterically demanding phosphanes, occurs during coupling reactions catalyzed by air-stable Pd1 dimers as shown in the scheme. As a result, the reactions of aryl chlorides and bromides with amines and boronic acids at room temperature are complete within a few minutes. 1-Ad = 1-adamantyl.
Identification of hydroxyhalobiphenyls as their methyl ethers by gas chromatography mass spectrometry.
Tulp,Olie,Hutzinger
, p. 310 - 316 (1977)
The mass spectra and gas chromatographic properties of 17 synthetic fluoro-, chloro- and bromomethoxy-biphenyls and 12 dichlorodimethoxybiphenyls have been examined. From this representative series it appears that the position of the methoxy group (ortho, meta and para to the biphenyl bond) in all monomethoxy compounds examined, and the positions of the two methoxy groups in most of the dimethoxy compounds, can be assigned unambiguously by their difference in fragmentation pattern. The value of this method was shown by metabolism experiments in which 4,4'-difluoro- and 4,4'-dibromobiphenyl were fed to rats and 4,4'-dichlorobiphenyl was administered to plants. All hydroxylated metabolites found were identified by gas chromatography mass spectrometry. Relationships between structure and gas chromatographic retention time of these compounds are discussed.
Preparation and characterization of new palladium complex immobilized on (chitosan)/PoPD biopolymer and its catalytic application in Suzuki cross-coupling reaction
Seyedi, Neda,Zahedifar, Mahboobeh
, (2021/11/17)
The present work reports the design, synthesis, and characterization of palladium complex immobilized on chitosan/poly(o-phenylenediamine) (CS-PoPD-Pd) for the catalytic application in the Suzuki–Miyaura C-C cross-coupling reaction through a nontoxic, inexpensive, eco-friendly, and practical method. Fourier-transform–infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), elemental mapping, X-ray diffraction (XRD), and inductively coupled plasma-optical emission spectrometry (ICP-OES) techniques were used for analyzing the prepared catalyst. Characterization studies showed that CS-PoPD-Pd was successfully synthesized according to our design. CS-PoPD-Pd composite demonstrated high product yield and high turnover number (TON) and turnover frequency (TOF) values with small catalyst loading for the Suzuki–Miyaura C-C cross-coupling reaction under mild reaction conditions. Besides, the synthesized CS-PoPD-Pd composite could be readily recycled and reused for at least five runs without discernible loss of its catalytic activity.
Nickel-Catalyzed Direct Cross-Coupling of Aryl Sulfonium Salt with Aryl Bromide
Chu, Xue-Qiang,Liu, Xiang,Ma, Na-Na,Rao, Weidong,Ren, Jing-Ao,Shen, Zhi-Liang
supporting information, (2022/03/27)
The direct cross-couplings of aryl sulfonium salts with aryl halides could be achieved by using nickel as a reaction catalyst. The reactions proceeded efficiently via C-S bond activation in the presence of magnesium turnings and lithium chloride in THF at ambient temperature to afford the corresponding biaryls in moderate to good yields, potentially serving as an attractive alternative to conventional cross-coupling reactions employing preprepared organometallic reagents.
Palladium supported on structurally stable phenanthroline-based polymer nanotubes as a high-performance catalyst for the aqueous Suzuki-Miyaura coupling reaction
Yang, Didi,Wang, Shuhui,Dan, Ting,Gao, Dashuang,Au, Chaktong,Zhang, Wanju,Zhang, Yan
, p. 12120 - 12128 (2021/07/19)
Though the Suzuki-Miyaura coupling reaction has intrinsic advantages in organic synthesis, it is still a challenging task to develop a highly active and truly heterogeneous catalyst for the aqueous Suzuki-Miyaura coupling reaction (SMR). In this work, a series of phenanthroline-based polymers (PBPs; PBP1 to PBP8) were synthesized by a simple one-step AlCl3-catalyzed Friedel-Crafts polymerization method. Systematic measurements of PBPs by N2adsorption-desorption isotherms, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA) show that most of the PBPs have a nanosheet morphology, except PBP8 which has both one-dimensional nanotubular morphology and large surface area (745 m2g?1). Benefitting from the porous nanotube morphology and the two N atoms contained in the phenanthroline unit of the polymer structure, polymer PBP8 shows adsorption effects and strong chelating stabilization on the Pd active metal (size, 2-5 nm). The Pd/PBP8 catalyst exhibits superior catalytic activity within 2 h (TOF value: 3077 h?1) and reusability (7 cycles) in the SMR with typical reactants such as bromobenzene, phenylboronic acid and the base of K3PO4.3H2O at 30 °C in a solvent mixture of water and ethanol (VH2O?:?Vethanol= 3?:?2).
