644-08-6Relevant articles and documents
Polymeric 2,2′-biquinolyl-containing NiII complexes as catalysts for the Suzuki reaction
Magdesieva,Nikitin,Polyakova,Yakimansky,Goikhman,Podeshvo
, p. 1193 - 1198 (2012)
The Suzuki reaction with polymeric Ni catalysts based on the biquinolyl-containing polyamic acids can be carried out under conditions close to the conditions used for the catalytic transformations in the presence of PdII complexes with the same polymeric ligands. However, the yields of the cross-coupling products on the Ni catalysts are somewhat lower than those obtained in the presence of palladium complexes. The yield of the cross-coupling product increases with the increase in the conformational mobility of the polymeric ligand. Unlike catalysis by palladium complexes, in catalytic transformations by nickel complexes activation of the catalyst is required. Such an activation can be carried out either by addition of chemical reducing agents or by applying the corresponding cathodic potential (-0.8 V relative to Ag/AgCl/KCl). The electrochemical activation was shown to lead to higher yields of the cross-coupling product than the use of chemical reducing agents.
Pd-Co3[Co(CN)6]2 hybrid nanoparticles: Preparation, characterization, and challenge for the Suzuki-Miyaura coupling of aryl chlorides under mild conditions
Li, Ren,Li, Ran,Wang, Changlai,Gao, Lei,Chen, Qianwang
, p. 539 - 544 (2015)
Because of their abundance and low cost, organo chlorides are the most desirable substrates from the industrial point of view in Suzuki-Miyaura cross-coupling reactions. However, catalytic application of Pd nanoparticles (NPs) for Suzuki coupling of aryl chlorides is still a challenge. Here, we design a novel catalyst by combining Pd NPs with Co3[Co(CN)6]2 nanocrystals for Suzuki-Miyaura coupling of aryl chlorides. This nanocatalyst demonstrated good activity (yield 86.2% at 80 °C), high TOF, great stability, easy separation, excellent reusability (initial rates were not reduced after five cycles) and low cost in Suzuki reactions.
C-Br activation of aryl bromides at Ni0(NHC)2: Stoichiometric reactions, catalytic application in Suzuki-Miyaura cross-coupling, and catalyst degradation
Zell, Thomas,Fischer, Peter,Schmidt, David,Radius, Udo
, p. 5065 - 5073 (2012)
Complex [Ni2(iPr2Im)4(COD)] (1) (iPr2Im = 1,3-diisopropylimidazolin-2-ylidene) is a very efficient catalyst for the Suzuki-Miyaura cross-coupling reaction of 4-bromotoluene with phenylboronic acid and also mediates the Ullmann-type homo-cross-coupling reaction of bromobenzene with a moderate efficiency. Stoichiometric reactions of complex 1 with aryl bromides (ArBr) at room temperature lead to mixtures of aryl bromo complexes of the type trans-[Ni( iPr2Im)2(Br)(Ar)] and the bis(bromo) complex trans-[Ni(iPr2Im)2(Br)2] 2. The complexes trans-[Ni(iPr2Im)2(Br)(Ar)] (for Ar = Ph 3, 4-MeC6H44, 4-Me(O)CC6H45, 4-MeOC6H46, 4-MeSC6H47, 4-Me 2NC6H48, 2-C5NH49) can be selectively synthesized by working at low temperatures and using a high dilution of the starting materials. A major deactivation pathway for trans-[Ni(iPr2Im)2(Br)(Ar)] was identified in the presence of aryl bromides. This deactivation process includes (i) the formation of trans-[Ni(iPr2Im)2(Br) 2] from trans-[Ni(iPr2Im)2(Br)(Ar)] (2) and ArBr and (ii) the formation of an imidazolium salt of the type 2[ iPr2Im-Ar]+[NiBr4]2- from trans-[Ni(iPr2Im)2(Br)2] (2) and ArBr. The reactions of complex 2 with a series of aryl halides at higher temperatures lead to the decomposition of the bis(carbene) nickel moiety with formation of the imidazolium salts 2[iPr2Im-Ar] +[NiBr2X2]2- (for X = I, Ar = Ph 10 and X = Br, Ar = Ph 11, 4-MeC6H412, 4-FC6H 413, 4-OSi(CH3)3-C6H414) in high yields.
Synthesis of brominated bisamides and their application to the suzuki coupling
Nobre, Sabrina M.,Cavalheiro, Valeria M.S.,Duarte, Leonardo S.
, p. 594 - 599 (2018)
Two brominated bisamides were developed by this protocol. Compounds were synthesized either by 4-bromobenzoyl chloride and ethylenediamine or by ortho-phenylenediamine. The choice of the diamine led to the desired products, which were characterized by IR,
(Ni,Mg)3Si2O5(OH)4 solid-solution nanotubes supported by sub-0.06 wt % palladium as a robust high-efficiency catalyst for Suzuki-Miyaura cross-coupling reactions
Zhu, Wancheng,Yang, Yan,Hu, Shi,Xiang, Guolei,Xu, Biao,Zhuang, Jing,Wang, Xun
, p. 6020 - 6031 (2012)
(Ni1-x,Mgx)3Si2O 5(OH)4 solid-solution nanotubes (NTs) with tunable compositions were hydrothermally synthesized by altering the molar ratio of Mg2+ to Ni2+. The as-synthesized NTs were loaded with sub-0.06 wt % palladium (Pd; ～0.045 wt %) for Suzuki-Miyaura (SM) coupling reactions between iodobenzene or 4-iodotoluene and phenylboronic acid. The (Ni,Mg)3Si2O5(OH)4 (Mg 2+:Ni2+ = 1.0:1.0) NTs supported by 0.045 wt % Pd promoted the iodobenzene-participated coupling reaction with a high yield of >99%, an excellent recycling catalytic performance during 10 cycles of catalysis with yields of ～99%, and also an extremely low Pd releasing level of ～0.02 ppm. High-activity Pd and PdO clusters, multitudes of dislocations, and defects and terraces contained within the NTs should contribute to the (Ni,Mg) 3Si2O5(OH)4 (Mg2+:Ni 2+ = 1.0:1.0) NTs supported by 0.045 wt % Pd as a robust, reusable, and high-efficiency catalyst for SM coupling reactions with an extremely low Pd releasing level. The present hydrothermally stable (Ni,Mg)3Si 2O5(OH)4 (Mg2+:Ni2+ = 1.0:1.0) solid-solution silicate NTs provided an ideal alternative tubular-structured support for noble- or transition-metal catalysts with low Pd loading, good recycling, and extremely low ppb levels of Pd release, which could also be extended to some other SM coupling reactions.
Pd-catalyzed Kumada-Corriu cross-coupling reactions at low temperatures allow the use of Knochel-type Grignard reagents
Martin, Ruben,Buchwald, Stephen L.
, p. 3844 - 3845 (2007)
A catalyst system able to operate at temperatures as low as -65 °C for the Pd-catalyzed Kumada-Corriu cross-coupling reaction is described. This unprecedented level of activity allows the use of highly functionalized (Knochel-type) Grignard reagents. Additionally, the tolerance of the protocol toward a wide variety of functional groups allows for the synthesis of valuable compounds, including heterocyclic or polyfluoro biaryls. Copyright
Suzuki cross-coupling reaction of aryl halides with arylboronic acids catalysed by Pd(II)-NaY zeolite
Bulut, Hatice,Artok, Levent,Yilmazu, Selahattin
, p. 289 - 291 (2003)
Pd(II)-exchanged NaY zeolite showed high activity in the Suzuki cross-coupling reactions of aryl bromides and iodides without added ligands. The DMF:water ratio, and the type and amount of base were found to be critical for the efficiency of the reaction. The catalyst is reusable after regeneration.
Synthesis of Pd nanocrystals in phosphonium ionic liquids without any external reducing agents
Kalviri, Hassan A.,Kerton, Francesca M.
, p. 681 - 686 (2011)
Trihexyl(tetradecyl)phosphonium ionic liquids (ILs) are found to support the formation of Pd(0) nanoparticles without the addition of reducing agents such as NaBH4. The resulting particles are highly crystalline and have been characterized by a range of techniques including TEM and XRD. Their sizes are in the range 7 ± 2 nm. The particle formation process is highly dependent on the anion of the IL with no nanoparticles observed when the chloride derivative was used. Particle shape could be controlled through varying the anion of the IL and the Pd(ii) precursor used. Palladium chloride reagents gave truncated octahedron shaped particles in trihexyl(tetradecyl)phosphonium dodecylbenzenesulfonate, whereas palladium acetate under the same conditions afforded a mixture of shapes including triangular plates. We propose that the presence of chloride anions in the reaction mixtures led to oxidative etching of the particles and that this process can be reduced in the presence of certain anion partners in the IL including bis(2,4,4-trimethylpentyl)phosphinate. Two possible reduction mechanisms based on reactions of the phosphonium cation are suggested for the formation of the Pd(0) species. The resulting nanoparticles are effective in catalyzing the Suzuki reaction of 4-bromotoluene and benzene boronic acid. The Royal Society of Chemistry.
Palladium Nanoparticles Anchored on Thiol Functionalized Xylose Hydrochar Microspheres: An Efficient Heterogeneous Catalyst for Suzuki Cross-Coupling Reactions
Huang, Pingquan,Zeng, Xiaoyan,Du, Fan,Zhang, Lei,Peng, Xinwen
, p. 1011 - 1019 (2020)
Abstract: Novel thiol functionalized xylose hydrochar microspheres supported palladium nanoparticles (C–SH–Pd) were synthesized by gentle heating of palladium (II) acetate and thiol functionalized xylose hydrochar (C–SH) in ethanol. The as-prepared C–SH–Pd exhibited high catalytic activity towards Suzuki reactions with a yield of high up to 100%. Moreover, it could be reused for at least five times without heavily loss of the catalytic activity. The amount of palladium entrapped on C-SH microspheres was measured by AAS and found to be 1.42?mmol/g. Leaching studies showed that the filtrate contained less than 0.2?ppm Pd. Due to the superior catalytic performance and stability of the C–SH–Pd catalyst, it can be exploited in other cross coupling reactions in the long run. Graphic Abstract: [Figure not available: see fulltext.].
Phosphine oxide polymer for water-soluble nanoparticles
Kim, Sang-Wook,Kim, Sungjee,Tracy, Joseph B.,Jasanoff, Alan,Bawendi, Moungi G.
, p. 4556 - 4557 (2005)
A phosphine oxide polymer was developed using bis(dichlorophosphino)ethane and poly(ethylene glycol). This polymer system was used to transfer various nanoparticles from organic solvents to water, retaining their physical properties and reactivities. Copyright
Palladium(0) nanoparticles encapsulated in diamine-modified glycidyl methacrylate polymer (GMA-CHDA) applied as catalyst of Suzuki-Miyaura cross-coupling reaction
Trzeciak, Anna M.,Mieczynska, Ewa,Ziolkowski, Jozef J.,Bukowski, Wiktor,Bukowska, Agnieszka,Noworol, Jaroslaw,Okal, Janina
, p. 1124 - 1130 (2008)
Cyclohexyldiamine-modified glycidyl methacrylate polymer (GMA-CHDA) in the form of gel-type beads was used to encapsulate Pd(0) nanoparticles 4-15 nm in diameter and applied as a new, reusable catalyst for the Suzuki-Miyaura cross-coupling reaction of 2- and 4-bromotoluene with phenylboronic acid. It was found that the precatalyst preparation methodology strongly influenced its catalytic activity. The best results (100% yield of the product) were obtained when GMA-CHDA was first treated with hydrazine (reducing agent for Pd(ii)) and next with PdCl2 solution. The new catalyst acts heterogeneously, and the post-reaction solution after catalyst separation is not catalytically active, suggesting that there is no leaching. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
Taylor et al.
, p. 6088 (1970)
Microwave-assisted synthesis of Pd nanoparticles and their catalysis application for Suzuki cross-coupling reactions
Zhang, Jian,Bai, Xuefeng
, p. 672 - 676 (2017)
Pd nanoparticles (PdNPs) were prepared via microwave-assisted chemical reduction method (PdNPs-MW) and a conventional chemical reduction method (PdNPs-C) using ethanol as the reducing agent in the presence of polyvinylpyrrolidone (PVP), respectively. The as-prepared PdNPs were characterized by UV–vis spectroscopy, TEM, XRD, and X-ray photoelectron spectroscopy analysis. The results showed that PdNPs- MW had a uniform structure and narrower size distribution with diameters of 3.6–5.4 nm. An obvious increase in size of the PdNPs was apparent for PdNPs-C. The PdNPs-MW demonstrated 68.7% yield toward the Suzuki cross-coupling reaction of 4-bromobenzonitrile and phenylboronic acid for 10 min with a higher turnover frequency of 41220 h-1 compared with the value of PdNPs-C (20580 h-1).
Arrested catalysis: Controlling Kumada coupling activity via a redox-active N-heterocyclic carbene
Tennyson, Andrew G.,Lynch, Vincent M.,Bielawski, Christopher W.
, p. 9420 - 9429 (2010)
Optimized syntheses for 1,3-dimesitylnaphthoquinimidazolium chloride [1H][Cl] and the corresponding silver-NHC complex [AgCl(1)] (2) were developed, enabling access to this versatile reagent in near-quantitative yield. Transmetalation from 2 to [NiCl2(PPh3)2], trans-[PdCl2(PhCN)2], or trans-[PtCl2(PhCN) 2] afforded the Group 10 complexes trans-[MCl2(1) 2] (3a-c, M) Ni, Pd, and Pt, respectively) in excellent overall yield (>95%) after three steps from commercially available starting materials. Electrochemical measurements indicated that the E1/2 and ΔE1/2 values for the quinone reduction couples were independent of the identity of the bridging transition metal in these complexes. Whereas attempts to isolate the reduced complexes were unsuccessful, UV/vis spectroelectrochemical analysis confirmed that electrochemical reduction of 3a-c in situ afforded optical difference spectra consistent with the formation of the expected reduced species. Complex 3a was found to catalyze the Kumada cross-coupling reaction between PhMgCl and a range of bromoarenes at room temperature. Addition of 2 equiv of cobaltocene (with respect to 3a) to the coupling reaction with bromotoluene caused a decrease in catalytic activity (from 4.7 × 10-5 to 2.7 × 10-6 s -1), which was attributed to the conversion of 3a to an arrested state. Subsequent introduction of ferrocenium tetrafluoroborate (2 equiv with respect to 3a) restored a significant degree of catalytic activity (k obs) 1.2 × 10-5 s-1). Redox-switching experiments performed over different time scales Revealed that the catalyst was stable in the reduced/inactive state and that extended durations in this state did not impede catalytic reactivation upon subsequent oxidation.
Effect of 2-substituents on allyl-supported precatalysts for the Suzuki-Miyaura reaction: Relating catalytic efficiency to the stability of palladium(I) bridging allyl dimers
Hruszkewycz, Damian P.,Guard, Louise M.,Balcells, David,Feldman, Nicola,Hazari, Nilay,Tilset, Mats
, p. 381 - 394 (2015)
One of the most commonly used classes of precatalysts for cross-coupling are Pd(II) complexes of the type (η3-allyl)Pd(L)Cl. Here, we report the first full investigation of how the steric and electronic properties of the 2-substituent affect th
Polystyrene-cross-linking Ortho-substituted triphenylphosphines: Synthesis, coordination properties, and application to Pd-catalyzed cross-coupling of aryl chlorides
Iwai, Tomohiro,Asano, Kiichi,Harada, Tomoya,Sawamura, Masaya
, p. 943 - 949 (2017)
Polystyrene-cross-linking triphenylphosphines having methyl groups as ortho substituents were synthesized. Coordination of the polymer-bound tri(o-tolyl)phosphine-type ligand toward a Pd(II) complex was investigated by 31PCP/MASNMR spectroscopi
Carbohydrate-substituted N-heterocyclic carbenes Palladium complexes: High efficiency catalysts for aqueous Suzuki–Miyaura reaction
Hu, Yunchi,Huang, Qing,Huang, Yanxia,Li, Jing,Wen, Xiaoming,Xie, Qian,Xie, Yongrong,Xu, Guohai,Zhou, Zhonggao
supporting information, (2022/02/10)
Metal complexes that contain carbohydrate-substituent (Carb-) N-heterocyclic carbenes (NHCs) ligand have demonstrated great success as catalysts for organic synthesis reactions. In this study, four new Carb-NHC-Pd complexes 2a-d were prepared and their catalytic activities for Suzuki–Miyaura reaction were evaluated. The Carb-NHC-Pd complex behaved as a general surfactant which leads to the formation of a temporary oil-in-water contact interface, thereby promoting the Suzuki–Miyaura reaction. A long hydrophobic alkyl chain (–nC16H33) was remotely linked to complex 2d, in which Carb-NHCs showed high electron-donating properties, and steric bulk with 1JCH constant of 1H NMR. Complex 2d exhibited a higher catalytic activity as compared with 2a (–nC2H5), 2b (–nC4H9), and 2c (–nC8H17). A series of fluorene-cored materials with different aryl groups were synthesized with high yields (34 examples, 91–99%) under the optimized reaction conditions.
One-Step Access to Heteroatom-Functionalized Imidazol(in)ium Salts
Pasyukov, Dmitry V.,Shevchenko, Maxim A.,Shepelenko, Konstantin E.,Khazipov, Oleg V.,Burykina, Julia V.,Gordeev, Evgeniy G.,Minyaev, Mikhail E.,Chernyshev, Victor M.,Ananikov, Valentine P.
supporting information, (2022/01/31)
Imidazolium salts have ubiquitous applications in energy research, catalysis, materials and medicinal sciences. Here, we report a new strategy for the synthesis of diverse heteroatom-functionalized imidazolium and imidazolinium salts from easily available 1,4-diaza-1,3-butadienes in one step. The strategy relies on a discovered family of unprecedented nucleophilic addition/cyclization reactions with trialkyl orthoformates and heteroatomic nucleophiles. To probe general areas of application, synthesized N-heterocyclic carbene (NHC) precursors were feasible for direct metallation to give functionalized M/carbene complexes (M=Pd, Ni, Cu, Ag, Au), which were isolated in individual form. The utility of the chloromethyl function for the postmodification of the synthesized salts and Pd/carbene complexes was demonstrated. The obtained complexes and imidazolium salts demonstrated good activities in Pd- or Ni-catalyzed model cross-coupling and C?H activation reactions.
