1625-92-9Relevant articles and documents
Immobilized palladium nanoparticles within polymers as active catalysts for Suzuki-Miyaura reaction
Chen, Ting,Mao, Fei,Qi, Zhengliang,Li, Yan,Chen, Rizhi,Wang, Yong,Huang, Jun
, p. 16899 - 16903 (2016)
A highly active and reusable catalyst Pd@PNP was developed for Suzuki-Miyaura reaction of aryl chlorides and bromides with aryl boronic acids, and the corresponding biphenyl compounds were obtained in good to excellent yields. Triphenylphosphine and palladium nanoparticles were immobilized in situ in the polymer formed from Pd catalyzed coupling of tris(4-bromophenyl)amine and benzene-1,4-diboronic acid. The immobilized triphenylphosphine enhanced the activity and the stability of the catalyst Pd@PNP, and the catalyst Pd@PNP can be reused at least 5 times with good activity. Functional groups, such as methoxyl, nitrile, tert-butyl, nitro, acyl and formyl groups, were well tolerated under the reaction conditions, and the corresponding products were obtained in high yields.
One-pot preparation of magnetic N-heterocyclic carbene-functionalized silica nanoparticles for the Suzuki-Miyaura coupling of aryl chlorides: Improved activity and facile catalyst recovery
Yang, Hengquan,Wang, Yunwei,Qin, Yong,Chong, Yanzhu,Yang, Qiaozhen,Li, Guang,Zhang, Li,Li, Wei
, p. 1352 - 1361 (2011)
Based on a reverse micelle strategy, we successfully synthesized new magnetic silica nanoparticles functionalized with a bulky N-heterocyclic carbene (N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, denoted as IPr) precursor through the co-condensation of IPr-bridged organosilane and tetraalkoxysilane in a one-pot reaction. TEM and SEM investigations revealed that the particle sizes of the synthesized materials were uniformly distributed in the range 15-30 nm, and could be tuned by varying the amount of siliceous precursors. FT-IR and XPS characterizations showed that the IPr ligand was successfully incorporated onto magnetic silica nanoparticles. Such materials show good coordination capability toward Pd(acac)2 (acac = acetylacetonate), leading to a higher loading in comparison with magnetic silica nanoparticles (without functionalization). This Pd-loaded material is active toward the Suzuki-Miyaura couplings of challenging aryl chlorides under relatively mild conditions (at 80°C). An 81% yield for biphenyl was achieved in the presence of 0.32 mol% of Pd within 8 h, using iso-propyl alcohol as a solvent and KOtBu as a base. The activity of the functionalized nanoparticles is much higher than that of mesoporous silica-based catalysts, as well as a commercial Pd/C catalyst. This catalyst can be easily isolated by using a magnetic field and directly used in the next reaction cycle without significant loss of its activity.
Polyfluorinated phosphine ligands in the room temperature Suzuki cross-coupling reactions
Yekta, Shahla,Cheung, Lawrence,Yudin, Andrei K.
, p. 8048 - 8051 (2007)
Polyfluorinated phosphine ligands can be obtained by regioselective nucleophilic aromatic substitution on tetrafluoronaphthalene derivatives. The ligand efficiency has been demonstrated in the room temperature Suzuki coupling reactions of aryl bromides an
The catalytic ability of various transition metals in the direct functionalization of aromatic C-H bonds
Li, Hu,Sun, Chang-Liang,Yu, Miao,Yu, Da-Gang,Li, Bi-Jie,Shi, Zhang-Jie
, p. 3593 - 3597 (2011)
From noble to normal: Many transition-metal complexes have shown a remarkable ability to catalyze the cross-coupling of aryl halides with arenes (see scheme). The formation of biaryls has thus been achieved using inexpensive, readily available, and sometimes nontoxic transition-metal complexes. Not only "noble" transition metals, but also many of the "normal" transition metals are able to promote the direct transformation of C-H bonds.
A self-supported palladium-bipyridyl catalyst for the Suzuki-Miyaura coupling in water
Osako, Takao,Uozumi, Yasuhiro
, p. 505 - 514 (2010)
A self-supported palladium catalyst (PdCI2BPy-Cu) was prepared via construction of a metal-organic framework (MOF) of a bipyridyl-palladium complex bearing carboxylic groups and a copper(II) linker. PdCI2BPy-Cu efficiently catalyzed the Suzuki-Miyaura coupling of phenyl halides with arylboronic acids in water under atmospheric conditions to afford the corresponding biaryl products in high yield. The catalyst was reused four times without loss of catalytic activity.
Pd–Ni bimetallic nanoparticles supported on ZrO2 as an efficient catalyst for Suzuki–Miyaura reactions
Zhang, Li-Jie,Yao, Xian,Sun, Ying-xin,Zhang, Jia-wei,Cai, Chun
, p. 419 - 423 (2018)
Pd–Ni bimetallic nanoparticles (BMNPs) supported on ZrO2 were prepared by an impregnation–reduction method. The BMNPs showed excellent catalytic performance in Suzuki carbon–carbon cross-coupling reactions and almost quantitative conversion of the substrates was obtained under mild conditions in the absence of ligand. The excellent catalytic performance of the bimetallic catalyst could be a result of the synergistic effect between the two metal components. The catalyst showed outstanding recyclability during the reaction process; no obvious decrease in catalytic performance was observed after five cycles.
Self-assembled Pd6L4 cage and Pd4L4 square using hydrazide based ligands: Synthesis, characterization and catalytic activity in Suzuki-Miyaura coupling reactions
Pradhan, Subhashis,John, Rohith P.
, p. 12453 - 12460 (2016)
A discrete Pd6L4Td-symmetric molecular cage and a discrete Pd4L4 square assembly were obtained using a coordination-driven self-assembly technique. The assembly, Pd6L4, was prepared via a face-directed method, utilising a 'cis-clipped' palladium(ii) species and a new C3 symmetric tripodal hydrazinic ligand. The Pd4L4 square assembly was prepared via an edge directed method, using the 'cis-clipped'-palladium(ii) species and a new C2 symmetric dipodal hydrazinic ligand. Both assemblies were characterised using multinuclear NMR and ESI-MS spectroscopic techniques and elemental analysis. The size of the assemblies were assigned from HR-TEM measurements, while DOSY NMR analysis established the presence of single component species in solution. Optimised structures obtained using Hartree-Fock calculations are in conformity with the experimental results. Both the assemblies show significant catalytic activity as heterogeneous catalysts for Suzuki-Miyaura coupling reactions under mild, aerobic and phosphine free conditions in aqueous ethanolic medium.
AlAr3(THF): Highly efficient reagents for cross-couplings with aryl bromides and chlorides catalyzed by the economic palladium complex of PCy3
Ku, Shih-Lun,Hui, Xin-Ping,Chen, Chien-An,Kuo, Yi-Ying,Gau, Han-Mou
, p. 3847 - 3849 (2007)
Novel and highly efficient cross couplings of aryl bromides and chlorides with AlAr3(THF) (Ar = Ph, 2,4,6-Me3C6H 2, 2-naphthyl or 4-Me3SiC6H4) catalyzed by the economic palladium catalyst of PCy3 are reported without the use of a base and under mild reaction conditions at room temperature or temperatures ≤60°C even for couplings of bulky aryl halides and the Al(2,4,6-Me3C6H2)3(THF) reagent. The Royal Society of Chemistry.
Water-Soluble Palladium(II) Sulfonated Thiosemicarbazone Complexes: Facile Synthesis and Preliminary Catalytic Studies in the Suzuki-Miyaura Cross-Coupling Reaction in Water
Matsinha, Leah C.,Mao, Jincheng,Mapolie, Selwyn F.,Smith, Gregory S.
, p. 4088 - 4094 (2015)
A series of mono- and binuclear sulfonated thiosemicarbazone PdII complexes have been synthesised and characterised using nuclear magnetic resonance spectroscopy, infrared spectroscopy, electrospray ionisation mass spectrometry and elemental analysis. The complexes display excellent water-solubility at room temperature and in addition, 1H and 31P{1H} NMR spectroscopic experiments reveal that the mononuclear complex 4 is very stable in water at 70 °C. Consequently, preliminary catalytic experiments show the water-soluble complexes to be efficient catalyst precursors in the Suzuki-Miyaura cross-coupling reaction in water. No evidence of homo-coupling was observed and the water-soluble complexes demonstrated versatility in coupling substrates containing various functional groups. Mono- and binuclear thiosemicarbazone complexes were synthesized and characterized. The mononuclear complexes are very stable in water and all the catalysts are active for the Suzuki-Miyaura cross-coupling reaction of various substrates. The mononuclear catalysts were more active than their binuclear analogues. Catalyst 4 could be recycled efficiently twice.
Highly active palladium catalysts for Suzuki coupling reactions
Wolfe, John P.,Singer, Robert A.,Yang, Bryant H.,Buchwald, Stephen L.
, p. 9550 - 9561 (1999)
Mixtures of palladium acetate and o-(di-tert-butylphosphino)biphenyl (4) catalyze the room-temperature Suzuki coupling of aryl bromides and aryl chlorides with 0.5-1.0 mol % Pd. Use of o-(dicyclohexylphosphino)biphenyl (2) allows Suzuki couplings to be carried out at low catalyst loadings (0.000001-0.02 mol % Pd). The process tolerates a broad range of functional groups and substrate combinations including the use of sterically hindered substrates. This is the most active catalyst system in terms of reaction temperature, turnover number, and steric tolerance which has been reported to date.
NHC-Pd complex heterogenized on graphene oxide for cross-coupling reactions and supercapacitor applications
Kandathil, Vishal,Siddiqa, Aisha,Patra, Abhinandan,Kulkarni, Bhakti,Kempasiddaiah, Manjunatha,Sasidhar,Patil, Shivaputra A.,Rout, Chandra Sekhar,Patil, Siddappa A.
, (2020)
N-heterocyclic carbene (NHC)-palladium(II) complex (GO@NHC-Pd) was synthesized on graphene oxide (GO) support via a simple and cost-effective multistep approach. The spectroscopic, microscopic, thermal, and surface analyses of GO@NHC-Pd confirmed the successful formation of the catalyst. The investigation of catalytic activity showed that GO@NHC-Pd was very effective in Suzuki–Miyaura as well as Hiyama cross-coupling. Being heterogeneous in nature, GO@NHC-Pd was recovered after each reaction cycle easily and reused for up to nine and six cycles in Suzuki–Miyaura and Hiyama cross-coupling, respectively, without significant loss of activity. Further exploration of the supercapacitor performance of GO@NHC-Pd catalyst assembled in a two-electrode cell configuration shown a maximum attained capacitance of 105.26 F/g at a current density of 0.1 A/g with good cycling stability of 96.89% over 2,500 cycles.
Magnetic Fe-Ni Alloy Catalyzed Suzuki Cross-Coupling Reactions of Aryl Halides with Phenylboronic Acid
Zhang, Rongzhao,Miao, Chengxia,Wang, Shoufeng,Xia, Chungu,Sun, Wei
, p. 142 - 145 (2013)
Alloy there matey! The inexpensive and readily prepared magnetic Fe-Ni alloy is employed in the Suzuki reactions of aryl halides with phenylboronic acid. The products are obtained in moderate to excellent yields in the absence of a reducing agent. The magnetic nature of the catalyst is beneficial for the separation of the products, but the recyclability of the catalyst is poor, probably as a result of oxidation and leaching.
Polyureas derived from CO2 and diamines: highly efficient catalysts for C-H arylation of benzene
Liu, Zhenghui,Yang, Zhenzhen,Hao, Leiduan,Liu, Xinwei,Zhang, Hongye,Yu, Bo,Liu, Zhimin
, p. 51 - 55 (2016)
Polyureas derived from CO2 and diamines were effective for C-H arylation of benzene in the presence of t-BuOK, producing biaryl products with various substituents in high yields up to 97%. Dual-activation of K+ and t-BuO-, and π,π-stacking interaction between the substrate and the polymer backbone may account for the superior activity.
[PdCl2{8-(di-tert-butylphosphinooxy)quinoline)}]: a highly efficient catalyst for Suzuki-Miyaura reaction
Scrivanti,Bertoldini,Matteoli,Antonaroli,Crociani
, p. 7611 - 7615 (2009)
The complex [PdCl2(P-N)] containing the basic and sterically demanding 8-(di-tert-butylphosphinooxy)quinoline ligand (P-N) is a highly efficient catalyst for the coupling of phenylboronic acid with aryl bromides or aryl chlorides. The influence of solvent and base has been investigated, the highest rates being observed at 110 °C in toluene with K2CO3 as the base. With aryl bromides the reaction rates are almost independent on the electronic properties of the para aryl substituents, on the contrary, reduced reaction rates are observed when bulky substituents are present on the substrate. Nevertheless the coupling of 2-bromo-1,3,5-trimethylbenzene with phenylboronic acid can be carried out to completion in 2 h using a catalyst loading of 0.02 mol %. Under optimized reaction conditions, turnover frequencies as high as 1900 h-1 can be obtained in the coupling of 4-chloroacetophenone with phenylboronic acid; lower reaction rates are obtained with substrates bearing EDG substituents on the aryl group.
Palladium(II)-exchanged hydroxyapatite-catalyzed Suzuki-Miyaura-type cross-coupling reactions with potassium aryltrifluoroborates
Masuyama, Yoshiro,Sugioka, Yutaka,Chonan, Shiori,Suzuki, Noriyuki,Fujita, Masahiro,Hara, Kenji,Fukuoka, Atsushi
, p. 81 - 85 (2012)
Palladium(II)-exchanged hydroxyapatite (PdHAP; Pd/Ca ratio = ca. 1/200) was prepared by ion-exchanging with Ca2+ from calcined hydroxyapatite (2.0 mmol) and Pd(NO3)2 (0.10 mmol) in water (150 mL) at 70 °C for 24 h. The PdHAP (1 mol% Pd to aryl bromides) functioned as a catalyst for the Suzuki-Miyaura-type cross-coupling reaction of aryl bromides and potassium aryltrifluoroborates with triphenylphosphine (1 mol%) and excess potassium carbonate at 50 °C in methanol under air. This cross-coupling reaction was found to proceed in water, while the rate was slow compared with that in methanol. The heterogeneous PdHAP catalyst was used ten times repeatedly at 50 °C in methanol under air, though its catalytic activity gradually declined. XRD and XRF analyses and TEM images revealed that most of palladium species would still be supported as isolated ions on the repeatedly used PdHAP, in spite of the changes of the structure and composition of PdHAP surface at the late stages in the repetitive uses and the partial leaching of Pd species at the initial stages in the repetitive uses. The gradual decline of the catalytic activity might be dependent on either the changes of PdHAP surface at the late stages or the partial leaching of Pd species at the initial stages. Still, heterogeneous PdHAP served as a reusable catalyst for Suzuki-Miyaura-type cross-coupling reaction with potassium aryltrifluoroborates.
A robust and efficient Pd3 cluster catalyst for the suzuki reaction and its odd mechanism
Fu, Fangyu,Xiang, Ji,Cheng, Hao,Cheng, Longjiu,Chong, Hanbao,Wang, Shuxin,Li, Peng,Wei, Shiqiang,Zhu, Manzhou,Li, Yadong
, p. 1860 - 1867 (2017)
The palladium-catalyzed Suzuki-Miyaura coupling reaction is one of the most versatile and powerful tools for constructing synthetically useful unsymmetrical aryl-aryl bonds. In designing a Pd cluster as a candidate for efficient catalysis and mechanistic investigations, it was envisaged to study a case intermediate between, although very different from, the "classic" Pd(0)Ln and Pd nanoparticle families of catalysts. In this work, the cluster [Pd3Cl(PPh2)2(PPh3)3]+[SbF6]- (abbreviated Pd3Cl) was synthesized and fully characterized as a remarkably robust framework that is stable up to 170 °C and fully air-stable. Pd3Cl was found to catalyze the Suzuki-Miyaura C-C crosscoupling of a variety of aryl bromides and arylboronic acids under ambient aerobic conditions. The reaction proceeds while keeping the integrity of the cluster framework all along the catalytic cycle via the intermediate Pd3Ar, as evidenced by mass spectrometry and quick X-ray absorption fine structure. In the absence of the substrate under the reaction conditions, the Pd3OH species was detected by mass spectrometry, which strongly favors the "oxo-Pd" pathway for the transmetalation step involving substitution of the Cl ligand by OH followed by binding of the OH ligand with the arylboronic acid. The kinetics of the Suzuki- Miyaura reaction shows a lack of an induction period, consistent with the lack of cluster dissociation. This study may provide new perspectives for the catalytic mechanisms of C-C cross-coupling reactions catalyzed by metal clusters.
An active and recyclable polystyrene-supported N-heterocyclic carbene-palladium catalyst for the Suzuki reaction of arylbromides with arylboronic acids under mild conditions
Kang, Tairan,Feng, Qiang,Luo, Meiming
, p. 2305 - 2308 (2005)
A novel polymer-supported imidazolium salt has been prepared from a bisimidazolium salt and cross-linked chloromethyl polystyrene. The polymer-supported N-heterocyclic carbene-palladium complex, generated from the supported bisimidazolium salt and Pd(OAc)2, efficiently catalyzed the Suzuki coupling reaction of aryl bromides and arylboronic acids under air in aqueous DMF solution at room temperature, giving biaryls in good to excellent yields. The catalyst could be reused several times still retaining high activity. Georg Thieme Verlag Stuttgart.
Nickel-catalyzed C(sp2)-C(sp2) cross coupling reactions of sulfur-functionalities and Grignard reagents
Someya, Chika I.,Weidauer, Maik,Enthaler, Stephan
, p. 424 - 431 (2013)
In the present study, the nickel-catalyzed carbon carbon bond formation of a range of sulfur containing substrates with Grignard reagents via desulfurization has been explored. After investigation of different reaction parameters with a well-defined nickel complex an excellent and easy-accessible pre-catalyst was found. The obtained system was capable to convert a broad scope of substrates under mild reaction conditions. Graphical Abstract: [Figure not available: see fulltext.]
Organocatalytic synthesis of (Het)biaryl scaffoldsviaphotoinduced intra/intermolecular C(sp2)-H arylation by 2-pyridone derivatives
Das, Tapas Kumar,Kundu, Mrinalkanti,Mondal, Biswajit,Ghosh, Prasanjit,Das, Sajal
, p. 208 - 218 (2021/12/29)
A uniqueN,O-bidentate ligand 6-oxo-1,6-dihydro-pyridone-2-carboxylic acid dimethylamide (L1) catalyzed direct C(sp2)-H (intra/intermolecular) arylation of unactivated arenes has been developed to expedite access to (Het)biaryl scaffolds under UV-irradiation at room temperature. The protocol tolerated diverse functional groups and substitution patterns, affording the target products in moderate to excellent yields. Mechanistic investigations were also carried out to better understand the reaction pathway. Furthermore, the synthetic applicability of this unified approach has been showcasedviathe construction of biologically relevant 4-quinolone, tricyclic lactam and sultam derivatives.
Structural and catalytic properties of the [Ni(BIPHEP)X2] complexes, BIPHEP = 2,2-diphenylphosphino-1,1-biphenyl; X = Cl, Br
Ioannou, Polydoros-Chrysovalantis,Grigoropoulos, Alexios,Stergiou, Konstantina,Raptopoulou, Catherine P.,Psycharis, Vassilis,Svoboda, Jan,Kyritsis, Panayotis,Vohlídal, Ji?í
, (2021/04/15)
The synthesis and catalytic properties in Kumada C–C coupling of the [Ni(BIPHEP)X2] complexes, X = Cl (1), Br (2), are described. The crystal structures of the BIPHEP ligand and 2 are also presented and compared with previously reported crystal structures of atropisomeric bidentate phosphine ligands (P,P) and related [M(P,P)X2] complexes (M = Ni, Pd, Pt). BIPHEP crystallizes in the C2/c space group, with both enantiomers present in the unit cell. This is consistent with BIPHEP being a “tropos” ligand. Complex 2 crystallizes in the P21/a space group. There are two symmetry-independent molecules in the asymmetric unit, namely 2a and 2b, in which the BIPHEP ligand adopts the S or the R configuration, respectively. Complexes 2a and 2b exhibit a severely tetrahedrally-distorted square planar NiP2Br2 coordination sphere, with a PNiP bite angle of 93.3° and 94.7°, respectively. The observed catalytic behavior of complexes 1 and 2 in the Kumada coupling between p-tert-butyl-halogenobenzene and p-tolylmagnesium chloride is benchmarked against that of [Ni(dppp)Cl2], dppp = 1,3-bis(diphenylphoshpino)propane. However, all three complexes are catalytically inactive in the Suzuki-Miyaura coupling reaction.
