5331-28-2Relevant academic research and scientific papers
Synthesis and characterization of nano-cellulose immobilized phenanthroline-copper (I) complex as a recyclable and efficient catalyst for preparation of diaryl ethers, N-aryl amides and N-aryl heterocycles
Aghili, Nora,Hosseinzadeh, Rahman,Mavvaji, Mohammad
, (2022/01/03)
Functionalized nanocellulose was prepared and employed for immobilization of phenanthroline-copper(I) complex to afford cellulose nanofibril grafted heterogeneous copper catalyst [CNF-phen-Cu(I)]. This nanocatalyst was well characterized using FT-IR, NMR, XRD, CHNS, AAS, TGA, EDX and SEM. The activities of the synthesized catalyst were examined in the synthesis of diaryl ethers via C-O cross-coupling of phenols and aryl iodides, as well as, the preparation of N-aryl amides and N-aryl heterocycles through C-N cross-coupling of amides and N-H heterocycle compounds with aryl halides. In this trend, various substrates containing electron-donating and electron-withdrawing groups were exploited to evaluate the generality of this catalytic protocol. Accordingly, the catalyst demonstrated remarkable catalytic efficiency for both C-N and C-O cross-coupling reactions, thereby resulting in good to excellent yields of the desired products. Furthermore, the recoverability experiments of the catalyst showed that it can be readily retrieved by simple filtration and successfully reused several times with negligible loss of its catalytic activity.
Ligand- and Counterion-Assisted Phenol O-Arylation with TMP-Iodonium(III) Acetates
Kikushima, Kotaro,Miyamoto, Naoki,Watanabe, Kazuma,Koseki, Daichi,Kita, Yasuyuki,Dohi, Toshifumi
, p. 1924 - 1928 (2022/03/27)
High reactivity of trimethoxyphenyl (TMP)-iodonium(III) acetate for phenol O-arylation was achieved. It was first determined that the TMP ligand and acetate anion cooperatively enhance the electrophilic reactivity toward phenol oxygen atoms. The proposed method provides access to various diaryl ethers in significantly higher yields than the previously reported techniques. Various functional groups, including aliphatic alcohol, boronic ester, and sterically hindered groups, were tolerated during O-arylation, verifying the applicability of this ligand- and counterion-assisted strategy.
Synergistic effect of copper nanocrystals-nanoparticles incorporated in a porous organic polymer for the Ullmann C-O coupling r–eaction
Gorginpour, Forough,Zali-Boeini, Hassan
, (2021/02/22)
A quinoxaline-based porous organic polymer (Q-POP) as a mesoporous organic copolymer was developed as a new platform for the immobilization of CuNPs and copper nanocrystals. The prepared materials were characterized by FT-IR, XRD, N2 adsorption-desorption isotherms, ICP, TGA, SEM, HR-TEM, EDX, and single-crystal X-ray crystallography. The obtained catalyst presented extraordinary catalytic activity towards Ullmann C–O coupling reactions with high surface area, hierarchical porosity, and excellent thermal and chemical stability. Due to its high porosity, and synergistic effect of copper nanocrystals incorporated in the polymer composite, the as-synthesized catalyst was successfully utilized for the Ullmann C–O coupling reaction of phenols and different aryl halides to prepare various diaryl ether derivatives. All types of aryl halides (except aryl fluorides) were screened in the Ullmann C–O coupling reaction with phenols to produce diaryl ethers in good to excellent yields (70–97 %), and it was found that aryl iodides have the best results. Besides, due to the strong interactions between CuNPs, N, and O-atoms of quinoxaline moiety existing in the polymeric framework, the copper leaching from the support was not observed. Furthermore, the catalyst was recycled and reused for five consecutive runs without significant activity loss.
Aromatic ether compound or the sulfhydryl compound
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Paragraph 0072; 0074; 0076; 0109, (2021/11/19)
[Problem] Aromatic ether compounds and aromatic sulfide compound of this new technology to[Solution] In general formula (1a), (1b), (1c) palladium or nickel compound or a phosphine compound represented by the compound comprising a transition metal compound in the presence of a transition metal catalyst, (A1) is represented by compounds having hydroxy carbon C a-OH or (A2) with a compound represented by the sulfhydryl carbon C a-SH, nitro group (- NO2 ) To react with an aromatic nitro compound (B), (A1) to the compound of the aromatic nitro compound (C1) or the reaction product of an aromatic ether compounds (B) hetero coupling (A2) of the compounds of the reaction product of an aromatic sulfide compound of an aromatic nitro compound (C2) generating (B) hetero coupling characterized by comprising the step of, aromatic ether compounds or aromatic sulfide compound. [Drawing] no
URJC-1-MOF as New Heterogeneous Recyclable Catalyst for C-Heteroatom Coupling Reactions
Mu?oz, Antonio,Leo, Pedro,Orcajo, Gisela,Martínez, Fernando,Calleja, Guillermo
, p. 3376 - 3380 (2019/07/04)
Guillermo Calleja and co-workers from @urjc describe URJC-1-MOF as a new heterogeneous recyclable catalyst for c-heteroatom coupling reactions. The capacity of copper-based URJC-1-MOF as a MOF catalyst in cross-coupling reactions has been evaluated, focusing on the Chan-Lam-Evans arylation-type reactions on amines and alcohols without extra additives or ligands. The extraordinary chemical and structural stability of URJC-1-MOF and its good specific surface, make this material a promising alternative to homogeneous Cu (II) catalysts for cross-coupling reactions. URJC-1-MOF showed a remarkable catalytic activity for cross-coupling C?N and C?O reactions, higher than other heterogeneous and homogeneous copper-based catalyst, such as CuO, HKUST-1, Cu?MOF-74, Cu(OAc)2 and CuSO4?5H2O. Moreover, its easy recovery by simple filtration and reusability in successive runs without any loss of activity and stability, demonstrates the potential of URJC-1-MOF as an alternative catalyst for this kind of reactions in different chemical media of industrial interest.
Ullmann Reaction Catalyzed by Heterogeneous Mesoporous Copper/Manganese Oxide: A Kinetic and Mechanistic Analysis
Mullick, Kankana,Biswas, Sourav,Kim, Chiho,Ramprasad, Ramamurthy,Angeles-Boza, Alfredo M.,Suib, Steven L.
, p. 10290 - 10297 (2017/09/12)
A heterogeneous copper oxide supported on mesoporous manganese oxide (meso Cu/MnOx) was explored for Ullmann-type cross-coupling reactions. An inverse micelle-templated evaporation-induced self-assembly method with in situ addition of copper was adopted to synthesize the mesoporous catalyst. Broad substrate scope and excellent functional group tolerability in C-O, C-N, and C-S bond formation reactions were observed using the optimized reaction conditions. The catalytic protocol was ligand free, and the catalyst was reusable without any significant loss of activity. The kinetic and Hammett analyses provided evidence for oxidative addition to a Cu(I) reaction center followed by nucleophilic addition and reductive elimination at the active copper oxide surface. Rate acceleration was observed for aryl halides with electron-withdrawing groups. The Hammett analysis determined ρ = +1.0, indicative of an oxidative addition, whereas the electronic effect in the phenol ring (ρ = -2.9) was indicative of coordination to a metal ion. Theoretically, the oxidative addition of the aryl halides is assisted by the ligand environment of the copper center. Relevant mechanistic implications are discussed on the basis of the experimental and computational results.
Copper-Catalyzed Diaryl Ether Formation from (Hetero)aryl Halides at Low Catalytic Loadings
Zhai, Yuntong,Chen, Xiaofei,Zhou, Wei,Fan, Mengyang,Lai, Yisheng,Ma, Dawei
, p. 4964 - 4969 (2017/05/12)
Diaryl formation is achieved by coupling phenols and (hetero)aryl halides under the catalysis of CuI/N,N′-bis(2-phenylphenyl) oxalamide (BPPO) or CuI/N-(2-phenylphenyl)-N′-benzyl oxalamide (PPBO) at 90 °C using DMF or MeCN as the solvent. Only 0.2-2 mol % CuI and ligand are required for complete conversion, which represents the lowest catalytic loadings for a general Cu/ligand-catalyzed diaryl ether formation.
Visible-light-mediated synthesis of diaryl ethers from arylboronic acids and diaryliodonium salts
Liu, Li,Tang, Jiaqi,Qiang, Jian,Li, Jian,He, Mingyang
, p. 261 - 264 (2016/07/06)
With visible-light irradiation, a simple and metal-free photocatalytic system for the synthesis of diaryl ethers from arylboronic acids and diaryliodonium salts has been developed. The reaction proceeded in high yield for a range of different substrates in the presence of eosin Y under mild reaction conditions.
CuI/oxalamide catalyzed couplings of (hetero)aryl chlorides and phenols for diaryl ether formation
Fan, Mengyang,Zhou, Wei,Jiang, Yongwen,Ma, Dawei
supporting information, p. 6211 - 6215 (2016/05/24)
Couplings between (hetero)aryl chlorides and phenols can be effectively promoted by CuI in combination with an N-aryl-N′-alkyl-substituted oxalamide ligand to proceed smoothly at 120 °C. For this process, N-aryl-N′-alkyl-substituted oxalamides are more effective ligands than bis(N-aryl)-substituted oxalamides. A wide range of electron-rich and electron-poor aryl and heteroaryl chlorides gave the corresponding coupling products in good yields. Satisfactory conversions were achieved with electron-rich phenols as well as a limited range of electron-poor phenols. Catalyst and ligand loadings as low as 1.5 mol % are sufficient for the scaled-up variants of some of these reactions. Aryl and alkyl: N-Aryl-N′-alkyl-substituted oxalamide ligands promote the CuI catalyzed coupling of (hetero)aryl chlorides and phenols at 120 °C more effectively than bis(N-aryl)-substituted oxalamides. A wide range of electron-rich and electron-poor aryl and heteroaryl chlorides were converted into the corresponding coupling products in good yields.
Interface Engineering in Two-Dimensional Heterostructures: Towards an Advanced Catalyst for Ullmann Couplings
Sun, Xu,Deng, Haitao,Zhu, Wenguang,Yu, Zhi,Wu, Changzheng,Xie, Yi
supporting information, p. 1704 - 1709 (2016/02/03)
The design of advanced catalysts for organic reactions is of profound significance. During such processes, electrophilicity and nucleophilicity play vital roles in the activation of chemical bonds and ultimately speed up organic reactions. Herein, we demonstrate a new way to regulate the electro- and nucleophilicity of catalysts for organic transformations. Interface engineering in two-dimensional heteronanostructures triggered electron transfer across the interface. The catalyst was thus rendered more electropositive, which led to superior performance in Ullmann reactions. In the presence of the engineered 2D Cu2S/MoS2 heteronanostructure, the coupling of iodobenzene and para-chlorophenol gave the desired product in 92 % yield under mild conditions (100 °C). Furthermore, the catalyst exhibited excellent stability as well as high recyclability with a yield of 89 % after five cycles. We propose that interface engineering could be widely employed for the development of new catalysts for organic reactions.
