324-74-3Relevant articles and documents
A water-soluble pyridyl-triazole ligand for aqueous phase palladium catalyzed Suzuki-Miyaura coupling
Amadio, Emanuele,Scrivanti, Alberto,Beghetto, Valentina,Bertoldini, Matteo,Alam, Md. Mahbubul,Matteoli, Ugo
, p. 21636 - 21640 (2013)
An environmentally friendly water-soluble ligand has been prepared by "clicking" 2-(azidomethyl)pyridine with but-3-ynyl sodium sulphate. In situ combination of the new ligand with [Pd(η3-C 3H5)Cl]2 (Pd:ligand =
Palladacycle from cyclometalation of the unsubstituted cyclopentadienyl ring in ferrocene: Synthesis, characterization, theoretical studies, and application to suzuki-miyaura reaction
Qian, Hengyu,Yin, Zhigang,Zhang, Tongyan,Yan, Shihai,Wang, Quanling,Zhang, Chunxia
, p. 6241 - 6246 (2014)
The ferrocenylimines of general formula [(η5-C5H5)Fe(η5-C5H4)-CH2N=CH-C(R)=CH-C6H5] with R = H (2a) and CH3 (2b) were conveniently prepared from ferrocenylmethylamine. Reaction of 2a,b with lithium tetrachloropalladate in methanol in the presence of anhydrous sodium acetate resulted in the formation of the di-μ-chloro-bridged heteroannular cyclopalladated complexes 3a,b via the unsubstituted ferrocenyl C-H bond activation of the related ligands. Treatment of 3a,b with triphenylphosphine gave Pd{[(η5-C5H4)Fe(η5-C5H4)CH2N=CH-CH=CH-C6H5]}ClPPh3 (4a) and Pd{[(η5-C5H4)Fe(η5-C5H4)-CH2N=CH-C(CH3)=CH-C6H5]}ClPPh3 (4b), respectively. The crystal structures of 4a,b confirmed the formation of a carbon-palladium bond by using a carbon atom in the unsubstituted cyclopentadienyl ring. Additionally, theoretical studies using density functional theory calculations were carried out in order to account for the regioselectivity of cyclometalation. As for the catalysts, using 0.1% of palladacycles 4a,b in the presence of K3PO4·7H2O as base exhibited excellent yields in the Suzuki-Miyaura coupling reaction of aryl bromides with phenylboronic acid.
Cross-coupling reactions catalyzed by P, O chelate palladium complexes at room temperature
Guo, Mengping,Jian, Fangfang,He, Ren
, p. 9017 - 9020 (2005)
A new catalytic system based on P, O chelate palladium complexes for cross-coupling reactions is described. These catalysts have all shown high activity and selectivity under mild reaction condition.
Palladium nanoparticles immobilized over Strawberry fruit extract coated Fe3O4 NPs: A magnetic reusable nanocatalyst for Suzuki-Miyaura coupling reactions
Hemmati, Saba,Yousefi, Mohammad,Salehi, Mirmehdi Hashemi,Amiri, Mahdis,Hekmati, Malak
, (2020)
This paper develops a green method for in situ decorated of palladium nanoparticles over Fe3O4 nanoparticles, by utilizing Strawberry fruit extract and ultrasound irradiations, with no use of any toxic reducing agent. The structure's characterization is represented via diverse analytical methods such as FT-IR, FE-SEM, TEM, WDX, ICP, EDS and XXPS. Catalytic efficiency of magnetic Fe3O4@Strawberry/Pd nanocatalyst is investigated in production of different biphenyls with good turnover frequencies (TOF) and turnover numbers (TON) through Suzuki coupling reactions. Furthermore, the catalyst could be recovered and reused 7 runs without considerable palladium leaching or alteration in its performance.
Magnetic Core–Shell to Yolk–Shell Structures in Palladium-Catalyzed Suzuki–Miyaura Reactions: Heterogeneous versus Homogeneous Nature
Li, Yinle,Zhang, Zhuqing,Fan, Tao,Li, Xiaoguang,Ji, Jin,Dong, Pei,Baines, Robert,Shen, Jianfeng,Ye, Mingxin
, p. 564 - 573 (2016)
This study describes a comparative investigation on the heterogeneous versus homogeneous nature of the Pd-catalyzed Suzuki–Miyaura cross-coupling reaction mechanism with specific magnetic hierarchical core–shell and yolk–shell structures. The hierarchical core–shell Fe3O4@SiO2-Pd@mCeO2 (m=mesoporous) catalyst contains a core of nonporous silica-sheltered magnetite (Fe3O4) nanoparticles (NPs), a transition layer of active palladium (Pd) NPs, and an outer shell of porous ceria (CeO2). The magnetic yolk–shell Fe3O4@h-Pd@mCeO2 (h=hollow) catalyst was prepared by selectively etching the nonporous silica interlayers. Notably, the results of the hot-filtration heterogeneity test, the effect of Pd concentration, and solid-phase poisoning, indicate that the two kinds of catalysts function in Pd-catalyzed Suzuki–Miyaura cross-coupling reactions through different catalytic mechanisms. Moreover, both catalysts demonstrated better catalytic activity than the Fe3O4@SiO2-Pd catalyst. This finding can be ascribed to the outermost CeO2 shell having a high concentration of trivalent cerium and oxygen vacancies, which gives rise to the increased electron density of Pd NPs, and a faster rate-determining step in the oxidative addition reaction for the Suzuki reaction. In addition, we propose a feasible mechanism elucidating the synergistic effect between the supporting CeO2 and active species.
The air-stable and highly efficient P, N-chelated palladium(II) complexes as catalysts for the Suzuki cross-coupling reaction at room temperature
Guo, Mengping,Jian, Fangfang,He, Ren
, p. 2033 - 2036 (2006)
Two air-stable P, N-chelated palladium(II) complexes have been evaluated as highly efficient and simple catalysts for Suzuki cross-coupling reaction between aryl bromides and arylboronic acids. They exhibit high activity and selectivity at room temperature.
Palladium(ii) complexes supported by PBP and POCOP pincer ligands: A comparison of their structure, properties and catalytic activity
Ding, Yazhou,Ma, Qiang-Qiang,Kang, Jiaxin,Zhang, Jie,Li, Shujun,Chen, Xuenian
, p. 17633 - 17643 (2019)
A Pd(ii) chloride complex supported by a Yamashita-Nozaki PBP pincer ligand, [C6H4-1,2-(NCH2PtBu2)2B]PdCl (1a), was synthesized. The structure, properties and catalytic activity of complex 1a were compared with those of the corresponding POCOP pincer complex [C6H3-2,6-(OPtBu2)2]PdCl (2a). It was found that the Pd centre in complex 1a is more electron rich and easier to be oxidized than that in complex 2a; complex 1a is a much better catalyst for Suzuki-Miyaura cross-coupling reactions than complex 2a. Starting from complexes 1a and 2a, two series of Pd(ii) pincer complexes bearing a SH, BH4, NCS, NCSe or N3 covalent ligand, [C6H4-1,2-(NCH2PtBu2)2B]PdY (Y = SH, 1b; BH4; 1c; NCS, 1d; NCSe, 1e; and N3, 1f) and [C6H3-2,6-(OPtBu2)2]PdY (Y = SH, 2b; BH4, 2c; NCS, 2d; NCSe, 2e; and N3, 2f), were synthesized and fully characterized. Single crystal X-ray diffraction analysis indicated that the Pd centre is less tightly chelated in PBP pincer complexes. The strong σ-donor ability of the PBP pincer ligand has little influence on the structure of the covalent ligand possessing both σ-donor and π-Acceptor properties. However, the stretching vibrational frequencies of NCS, NCSe and N3 ligands and the coordination mode of the BH4 ligand are significantly different in these two types of palladium pincer complexes.
Synthesis of a palladium complex bearing 2-phenylbenzothiazole and its application to Suzuki–Miyaura coupling reaction
Kosuru, Someswara Rao,Lai, Hsin-Yu,Yang, Chien-Yi,Senadi, Gopal Chandru,Lai, Yi-Chun,Chen, Hsuan-Ying
, p. 110 - 113 (2019)
The palladacycle complex [LsPdOAc]2 bearing 2-phenyl benzothiazole was synthesized and characterized by NMR and X-ray crystallography. [LsPdOAc]2 was used as a catalyst in the Suzuki–Miyaura cross coupling reaction of 4-bromotoluene with phenylboronic acid, which resulted in a conversion of >90% with 5 mol% of the Pd complex within 10 min at 60°C.
Synthesis of 18F-labelled biphenyls via SUZUKI cross-coupling with 4-[18F]fluoroiodobenzene
Steiniger, Bjoern,Wuest, Frank R.
, p. 817 - 827 (2006)
The SUZUKI reaction of organoboron compounds with 4-[18F] fluoroiodobenzene has been developed as a novel radiolabelling technique in 18F chemistry. The cross-coupling reaction of p-tolylboronic acid with 4-[18F]fluoroiodobenzene was used to screen different palladium complexes, bases and solvents. Optimized reaction conditions (Pd 2(dba)3, Cs2CO3, acetonitrile, 60°C for 5 min) were further applied to the synthesis of various 18F-labelled biphenyls bearing different functional groups. The reaction proceeded in excellent radiochemical yields of up to 94% within 5 min while showing good compatibility to many functional groups. Copyright
Palladium(ii) and palladium(ii)-silver(i) complexes with N-heterocyclic carbene and zwitterionic thiolate mixed ligands: synthesis, structural characterization and catalytic properties
Wang, Yu-Ting,Gao, Bin-Bin,Wang, Fan,Liu, Shi-Yuan,Yu, Hong,Zhang, Wen-Hua,Lang, Jian-Ping
, p. 1832 - 1839 (2017)
The integration of a geometrically rigid Pd(ii), a coordinatively monotonous N-heterocyclic carbene 1,3-dimethylimidazoline-2-ylidene (IMe), and a flexible zwitterionic thiolate 4-(trimethylammonio)benzenethiolate (Tab) affords a class of Pd-IMe-Tab complexes with various nuclearities, namely, trans-[Pd(IMe)2(Tab)2](OTf)2 (2, mononuclear), cis-[Pd(IMe)2(Tab)2](OTf)(Cl) (3a, mononuclear), cis-[Pd(IMe)2(Tab)2](PF6)2·MeCN (3b·MeCN, mononuclear), [Pd2(IMe)4(Tab)2](PF6)4·2MeCN (4·2MeCN, dinuclear) and [Pd4(IMe)4(Tab)6](OTf)6(Cl)2 (5, tetranuclear). Further presence of Ag(i) in the assembly provides a heterometallic octanuclear cluster of [Pd4Ag4(IMe)8(Tab)10](PF6)12 (6). Compounds 2-6 are formed by the reaction of trans-Pd(IMe)2Cl2 (1) with various additional reagents via different reaction pathways. These compounds are characterized by means of FT-IR, 1H and 13C NMR, ESI-MS, elemental analysis and X-ray crystallography. Notably, the skeleton of compound 5 features a [Pd4S4] parallelogram wherein each of the four Pd(ii) centers bisects the edge defined by the S atoms. The main skeleton of compound 6 is an oval-shaped Pd4Ag4S10 unit, featuring an edge-fused norbornane-like (Pd2Ag4S6) framework appended by two additional PdS2 motifs at the polar positions. Compounds 5 and 6 also feature Pd?Pd (5), Pd?Ag and Ag?Ag (6) interactions. Compound 5 as a representative example is highly effective at catalyzing Suzuki-Miyaura couplings in water, highlighting the potential of applying these types of homo- and heterometallic clusters as catalysts for organic transformations in environmentally benign media.
Synthesis and Bond Activation Chemistry of Palladium(II) Pincer Complexes with a Weakly Coordinating Side Arm
Prakasham,Vigalok, Arkadi,Vedernikov, Andrei N.
, p. 634 - 641 (2022/03/02)
A series of Pd(II) aryl complexes of a PNO-type pincer ligand bearing a weakly coordinated benzofuran side arm has been prepared. Crystallographic studies showed very long Pd-O distances of more than 2.3 ?, which is significantly longer than the Pd-O distances in structurally similar PNO-Pd complexes with an exocylic oxygen donor. Crystallographic and 19F NMR solution studies of complexes containing electron-donating (OMe) and electron-withdrawing (CF3) substituents in the position para to the benzofuran oxygen atom revealed the dependence of the Pd-O interactions on the nature of the aromatic group at the Pd center. The ability to influence these interactions by changing the electron density at the metal was demonstrated in the stoichiometric Sonogashira-type cross-coupling reactions between the Pd complexes and phenylacetylene, which proceed via a reversible aromatization/dearomatization of the pincer ligand. Complexes with the electron-poor CF3 group showed higher reactivity in comparison to their electron-neutral or -rich analogues. DFT studies of these systems provided further mechanistic insight into the origin of the observed reactivity patterns.
Biaryl Coupling of Aryldiazonium Salts and Arylboronic Acids Catalysed by Gold
Medina-Mercado, Ignacio,Porcel, Susana
, (2022/03/15)
A gold-catalysed coupling of aryldiazonium salts with arylboronic acids is described. The reactions proceed in satisfactory yields under irradiation with blue LEDs in the presence of KF and a catalytic amount of ascorbic acid. Notably, 4-nitrobenzendiazonium tetrafluoroborate is sufficiently reactive to undergo the coupling with a variety of arylboronic acids in the absence of aryl radical initiators. The coupling is applicable for electron-donating and electron-withdrawing groups present at the para, ortho, and meta positions of both substrates.
New Nickel-Based Catalytic System with Pincer Pyrrole-Functionalized N-Heterocyclic Carbene as Ligand for Suzuki-Miyaura Cross-Coupling Reactions
Guo, Zhifo,Lei, Xiangyang
supporting information, (2021/09/11)
A new catalytic system with Ni(NO3)2·6H2O as the catalyst and a pincer pyrrole-functionalized N-heterocyclic carbene as the ligand was employed in the Suzuki-Miyaura cross-coupling reactions of aryl iodides with arylboronic acids. With 5 mol% catalyst, the catalytic reactions proceeded at 160 °C, giving coupling products in isolated yields of up to 94% in short reaction times (1-4 h). The system worked efficiently with aryl iodides bearing electron-donating or electron-withdrawing groups and arylboronic acids with electron-donating groups. Steric effects were observed for both aryl iodides and arylboronic acids. It is proposed that the reactions underwent a Ni(I)/Ni(III) catalytic cycle.
