92-86-4Relevant articles and documents
Functionalized NHC-incorporated Te?Fe?Cu clusters: Facile synthesis, electrochemistry, and catalytic reaction
Shieh, Minghuey,Liu, Yu-Hsin,Li, Yu-Huei,Lin, Chien-Nan,Wang, Chih-Chin
, p. 161 - 169 (2018)
Two novel TeFe3(CO)9-containing functionalized NHC dicopper complexes, [TeFe3(CO)9{Cu(Me2-bimy)}2] (1) and [TeFe3(CO)9{Cu(iPr2-bimy)}2] (2), were prepared from the reaction of the ternary Te?Fe?Cu complex [TeFe3(CO)9{Cu(MeCN)}2] with bis-N-methyl- or bis-N-isopropyl-substituted benzimidazol-2-ylidene (Me2-bimy or iPr2-bimy) under appropriate conditions, respectively. X-ray analysis showed that Me2-bimy-introduced complex 1 displayed a TeFe3(CO)9Cu(Me2-bimy) trigonal-bipyramidal core geometry having the Fe2Cu face capped by a Cu(Me2-bimy) fragment with the two bonded Cu atoms, whereas the bulkier iPr2-bimy-incorporated complex 2 exhibited a similar TeFe3(CO)9Cu(iPr2-bimy) core having the Fe3 triangle coordinated by a Cu(iPr2-bimy) fragment with the two unbonded Cu atoms. On the other hand, when [TeFe3(CO)9{Cu(MeCN)}2] reacted with the 4,5-dichloro-substituted 1,3-dimethylimidazolium salt (Me2-Cl2-imy·HI) in the presence of KOtBu, a different type of [TeFe3(CO)9{Cu(Me2-Cl2-imy)}2] (3) was produced in good yields. Cluster 3 was shown to possess a tetrahedral TeFe3 core geometry in which the two Fe?Fe edges were each bridged by a Cu(Me2-Cl2-imy) group. According to solid-state packings, complex 1 revealed a cluster-based 3D-supramolecular framework and complexes 2 and 3 each formed a 1D-supramolecular chain, which was stabilized by intermolecular C?H…O interactions between COs and CH moieties of the corresponding NHC ligands. Further, these di-Cu(I) based complexes 1?3 exhibited catalytic activities toward the homocoupling of arylboronic acid with high yields. Importantly, the catalytic efficiencies of this series of functionalized NHC-incorporated TeFe3(CO)9Cu2-based complexes perfectly paralleled the ease of their first oxidation and the greater electron density of the carbene atom in the NHC ligands, which was elucidated by electrochemistry, 13C NMR, and DFT calculations.
Pd-Catalyzed desulfitative arylation of olefins by: N -methoxysulfonamide
Ojha, Subhadra,Panda, Niranjan
supporting information, p. 1292 - 1298 (2022/02/19)
A novel Pd-catalyzed protocol for the desulfitative Heck-type reaction of N-methoxy aryl sulfonamides with alkenes was reported. The cross-coupling reaction was performed successfully with a variety of olefins to obtain aryl alkenes. Different substituents on the aromatic ring of N-methoxysulfonamides were also found to be compatible with the reaction conditions. Expectedly, the reaction proceeds through CuCl2-promoted generation of the nitrogen radical and subsequent desulfonylation under thermal conditions to afford the aryl radical for the Pd-catalyzed coupling reaction. N-Methoxysulfonamide was further exploited for the synthesis of symmetrical biaryls in the presence of CuCl2. This journal is
Silk?Fibroin-Supported Palladium Catalyst for Suzuki-Miyaura and Ullmann Coupling Reactions of Aryl Chlorides
Albano, Gianluigi,Farinola, Gianluca M.,Giannini, Cinzia,Musio, Roberta,Omenetto, Fiorenzo G.,Rizzo, Giorgio,Sibillano, Teresa
supporting information, (2022/02/03)
Recently, we have reported the preparation of a silk fibroin-supported Palladium catalyst (Pd/SF) and its use in the Suzuki-Miyaura cross-coupling of aryl iodides. Since its synthetic applicability and structural features are still far from being fully ex
Porphyrin n-pincer pd(Ii)-complexes in water: A base-free and nature-inspired protocol for the oxidative self-coupling of potassium aryltrifluoroborates in open-air
Hanafiah, Marlia M.,Lakkaboyana, Sivarama Krishna,Lakshmidevi, Jangam,Marella, Ravi Kumar,Naidu, Bandameeda Ramesh,Prasad, Sana Siva,Venkateswarlu, Katta
, (2021/09/13)
Metalloporphyrins (and porphyrins) are well known as pigments of life in nature, since representatives of this group include chlorophylls (Mg-porphyrins) and heme (Fe-porphyrins). Hence, the construction of chemistry based on these substances can be based on the imitation of biological systems. Inspired by nature, in this article we present the preparation of five different porphyrin, meso-tetraphenylporphyrin (TPP), meso-tetra(p-anisyl)porphyrin (TpAP), tetra-sodium meso-tetra(p-sulfonatophenyl)porphyrin (TSTpSPP), meso-tetra(m-hydroxyphenyl)porphyrin (TmHPP), and meso-tetra(m-carboxyphenyl)porphyrin (TmCPP) as well as their N-pincer Pd(II)-complexes such as Pd(II)-meso-tetraphenylporphyrin (PdTPP), Pd(II)-meso-tetra(p-anisyl)porphyrin (PdTpAP), Pd(II)-tetrasodium meso-tetra(p-sulfonatophenyl)porphyrin (PdTSTpSPP), Pd(II)-meso-tetra(m-hydroxyphenyl)porphyrin (PdTmHPP), and Pd(II)-meso-tetra(m-carboxyphenyl)porphyrin (PdTmCPP). These porphyrin N-pincer Pd(II)-complexes were studied and found to be effective in the base-free self-coupling reactions of potassium aryltrifluoroborates (PATFBs) in water at ambient conditions. The catalysts and the products (symmetrical biaryls) were characterized using their spectral data. The high yields of the biaryls, the bio-mimicking conditions, good substrate feasibility, evading the use of base, easy preparation and handling of catalysts, and the application of aqueous media, all make this protocol very attractive from a sustainability and cost-effective standpoint.
Pd-catalyzed oxidative homocoupling of arylboronic acids in WEPA: A sustainable access to symmetrical biaryls under added base and ligand-free ambient conditions
Appa, Rama Moorthy,Lakshmidevi, Jangam,Naidu, Bandameeda Ramesh,Venkateswarlu, Katta
, (2021/01/11)
Symmetrical and unsymmetrical biaryls comprises a diverse class of biologically eloquent organic compounds. We herein report, a quick and eco-friendly protocol for the synthesis of biaryls by an oxidative (aerobic) homocoupling of arylboronic acids (ABAs) using Pd(OAc)2 in water extract of pomogranate ash (WEPA) as an efficient agro-waste(bio)-derived aqueous (basic) media. The reactions were executed at ambient aerobic conditions in the absence of external base and ligand to result symmetrical biaryls in excellent yields. The use of renewable media with an effective exploitation of waste, short reaction times, excellent yields of products, easy separation of the products, unnecessating the external base, oxidant, ligand or volatile organic solvents and ambient reaction conditions are the vital insights of the present protocol.
"benchtop" Biaryl Coupling Using Pd/Cu Cocatalysis: Application to the Synthesis of Conjugated Polymers
Minus, Matthew B.,Moor, Sarah R.,Pary, Fathima F.,Nirmani,Chwatko, Malgorzata,Okeke, Brandon,Singleton, Josh E.,Nelson, Toby L.,Lynd, Nathaniel A.,Anslyn, Eric V.
supporting information, p. 2873 - 2877 (2021/05/05)
Typically, Suzuki couplings used in polymerizations are performed at raised temperatures in inert atmospheres. As a result, the synthesis of aromatic materials that utilize this chemistry often demands expensive and specialized equipment on an industrial scale. Herein, we describe a bimetallic methodology that exploits the distinct reactivities of palladium and copper to perform high yielding aryl-aryl dimerizations and polymerizations that can be performed on a benchtop under ambient conditions. These couplings are facile and can be performed by simple mixing in the open vessel. To demonstrate the utility of this method in the context of polymer synthesis: polyfluorene, polycarbazole, polysilafluorene, and poly(6,12-dihydro-dithienoindacenodithiophene) were created at ambient temperature and open to air.
N-Methylphenothiazine S-Oxide Enabled Oxidative C(sp2)–C(sp2) Coupling of Boronic Acids with Organolithiums via Phenothiaziniums
Yoshida, Tatsuki,Honda, Yuki,Morofuji, Tatsuya,Kano, Naokazu
, p. 9664 - 9668 (2021/12/17)
Herein, we report the development of a transition-metal-free oxidative C(sp2)–C(sp2) coupling of readily available boronic acids and organolithiums via phenothiazinium ions. Various biaryl, styrene, and diene derivatives were obtained using this reaction system. The key to this process is N-methylphenothiazine S-oxide (PTZSO), which allows efficient conversion of boronic acids to phenothiazinium ions. The mechanism of phenothiazinium formation using PTZSO was investigated using theoretical calculations and experiments, which provided insight into the unique reactivity of PTZSO.
Exploring the coordination confinement effect of divalent palladium/zero palladium doped polyaniline-networking: As an excellent-performance nanocomposite catalyst for C-C coupling reactions
Liang, Yanping,Liu, Wanyi,Song, Manrong,Sun, Yanyan,Wang, Gang,Wu, Zhiqiang,Zhan, Haijuan
, p. 177 - 188 (2020/03/17)
A pre-formed catalyst Pd2+/PANI composite for C-C coupling reaction was synthesized by combining the self-stabilized dispersion polymerization method with the in-situ composite material. Experiments have confirmed that the relatively high reduced structure (75%) in the polyaniline carrier is more favorable for the coupling reaction. Raman spectroscopy, solid nuclear magnetic, and X-ray photoelectron spectroscopy were performed to characterize the structures. The pre-formed catalyst has uniform coordination of divalent palladium and nitrogen in different valence states of the carrier polyaniline, which shows a good synergistic effect in the catalytic Ullmann reaction, and greatly reduces the use of reducing agents such as hydrazine hydrate. Compared with other studies, we analyzed the catalytic reaction mechanism in detail through real-time online infrared and XPS characterization. The results show that the divalent palladium in the catalyst and the zero-valent palladium generated by the in-situ reaction synergistically promote the reaction, while the polyaniline support acts as a stabilizer and dispersant, which prevents the agglomeration of the metal particles and prolongs increased catalyst life. The prepared Pd2+/PANI composites will become the most attractive alternative to traditional organic materials due to their wide applicability, high catalytic activity, stable recycling and relatively low price. This work provides a new theoretical basis for the understanding of the essential driving force of PANI catalytic activity and the cognition of the micro mechanism of action.
Triptycenyl Sulfide: A Practical and Active Catalyst for Electrophilic Aromatic Halogenation Using N-Halosuccinimides
Nishii, Yuji,Ikeda, Mitsuhiro,Hayashi, Yoshihiro,Kawauchi, Susumu,Miura, Masahiro
supporting information, p. 1621 - 1629 (2020/02/04)
A Lewis base catalyst Trip-SMe (Trip = triptycenyl) for electrophilic aromatic halogenation using N-halosuccinimides (NXS) is introduced. In the presence of an appropriate activator (as a noncoordinating-anion source), a series of unactivated aromatic compounds were halogenated at ambient temperature using NXS. This catalytic system was applicable to transformations that are currently unachievable except for the use of Br2 or Cl2: e.g., multihalogenation of naphthalene, regioselective bromination of BINOL, etc. Controlled experiments revealed that the triptycenyl substituent exerts a crucial role for the catalytic activity, and kinetic experiments implied the occurrence of a sulfonium salt [Trip-S(Me)Br][SbF6] as an active species. Compared to simple dialkyl sulfides, Trip-SMe exhibited a significant charge-separated ion pair character within the halonium complex whose structural information was obtained by the single-crystal X-ray analysis. A preliminary computational study disclosed that the πsystem of the triptycenyl functionality is a key motif to consolidate the enhancement of electrophilicity.
Green-Synthesized Nickel Nanoparticles on Reduced Graphene Oxide as an Active and Selective Catalyst for Suzuki and Glaser-Hay Coupling Reactions
Murugan, Karthik,Nainamalai, Devarajan,Kanagaraj, Pavithara,Nagappan, Saravana Ganesan,Palaniswamy, Suresh
, (2020/07/09)
A mild and benign methodology to syntheses biaryls and 1,3-diynes has been demonstrated using the nickel nanoparticles supported on reduced graphene oxide (RGO-Ni) as a heterogeneous catalyst which is prepared using green reagents. A series of substituted biaryls and 1,3-diynes has been synthesised in good to excellent yields through C-C homocoupling reaction of arylboronic acids and terminal alkynes respectively using 1,4-dioxane as a benign solvent. The present ligand-free catalytic system proceeds smoothly under mild conditions, avoids noble and stoichiometric metal reagents and tolerates sensitive functional groups. Also has a wide substrate scope and feasible with other nitrogen and sulphur containing heteroaryl boronic acids. Hot filtration test unambiguously proves the true heterogeneity of the catalyst and which support for the further reusability of the catalyst for several times without any change in the activity. The easy preparation and simple magnetic separation, stability and reusability reveal that as-prepared RGO-Ni as a versatile catalyst for the synthesis of polyaromatic compounds both in academia and industries. Highlights: Green-synthesized RGO-Ni nanocomposite used as a heterogeneous catalyst for Suzuki type (C-C) and Glaser–Hay (C ≡ C) homocoupling coupling reactions. Ligand-free catalytic system and avoids noble and stoichiometric metal reagents Short reaction time with a minimum catalyst (nickel) loading RGO-Ni nanocomposite is highly stable, reusable, and magnetically retrievable.
