- Visible Light Induced Aerobic Coupling of Arylboronic Acids Promoted by Hydrazone
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A visible-light-induced oxidative coupling of arylboronic acids has been developed for the synthesis of biaryls. The reaction that employs polydentate hydrazones as the bifunctional catalyst works smoothly under room temperature. It is compatible with a w
- Xia, Hongyu,Wang, Ganghu,Zhao, Dongbo,Zhu, Chunyin
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supporting information
p. 922 - 929
(2022/02/10)
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- Zirconium-redox-shuttled cross-electrophile coupling of aromatic and heteroaromatic halides
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Transition metal-catalyzed cross-electrophile coupling (XEC) is a powerful tool for forging C(sp2)–C(sp2) bonds in biaryl molecules from abundant aromatic halides. While the synthesis of unsymmetrical biaryl compounds through multimetallic XEC is of high synthetic value, the selective XEC of two heteroaromatic halides remains elusive and challenging. Herein, we report a homogeneous XEC method, which relies on a zirconaaziridine complex as a shuttle for dual palladium-catalyzed processes. The zirconaaziridine-mediated palladium (ZAPd)-catalyzed reaction shows excellent compatibility with various functional groups and diverse heteroaromatic scaffolds. In accord with density functional theory (DFT) calculations, a redox transmetallation between the oxidative addition product and the zirconaaziridine is proposed as the crucial elementary step. Thus, cross-coupling selectivity using a single transition metal catalyst is controlled by the relative rate of oxidative addition of Pd(0) into the aromatic halide. Overall, the concept of a combined reducing and transmetallating agent offers opportunities for the development of transition metal reductive coupling catalysis.
- Fu, Yue,Liu, Fang-Jie,Liu, Peng,Tang, Jian-Tao,Toste, F. Dean,Wu, Ting-Feng,Ye, Baihua,Zhang, Yue-Jiao
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supporting information
p. 1963 - 1974
(2021/07/07)
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- Reductive Coupling of Aryl Halides via C—H Activation of Indene
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This paper describes the first case of a reductive coupling reaction with indene, a non-heteroatom olefin used as a reducing agent. The scope of the substrate is wide. The homo-coupling, cross-coupling, and synthesis of 12 and 14-membered rings were realized. The control experiment, indene-product curve and density functional theory calculations showed that the η3-palladium indene intermediate was formed by C—H activation in the presence of cesium carbonate. We speculate that the final product was obtained through a Pd (IV) intermediate or aryl ligand exchange. In addition, we excluded the formation of palladium anion (Pd(0)?) intermediates.
- Zhang, Bo-Sheng,Yang, Ying-Hui,Wang, Fan,Gou, Xue-Ya,Wang, Xi-Cun,Liang, Yong-Min,Li, Yuke,Quan, Zheng-Jun
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p. 1573 - 1579
(2021/05/28)
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- Tandem Mn–I Exchange and Homocoupling Processes Mediated by a Synergistically Operative Lithium Manganate
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Pairing lithium and manganese(II) to form lithium manganate [Li2Mn(CH2SiMe3)4] enables the efficient direct Mn–I exchange of aryliodides, affording transient (aryl)lithium manganate intermediates which in turn undergo spontaneous C?C homocoupling at room temperature to furnish symmetrical (bis)aryls in good yields under mild reaction conditions. The combination of EPR with X-ray crystallographic studies has revealed the mixed Li/Mn constitution of the organometallic intermediates involved in these reactions, including the homocoupling step which had previously been thought to occur via a single-metal Mn aryl species. These studies show Li and Mn working together in a synergistic manner to facilitate both the Mn–I exchange and the C?C bond-forming steps. Both steps are carefully synchronized, with the concomitant generation of the alkyliodide ICH2SiMe3 during the Mn–I exchange being essential to the aryl homocoupling process, wherein it serves as an in situ generated oxidant.
- Uzelac, Marina,Mastropierro, Pasquale,de Tullio, Marco,Borilovic, Ivana,Tarrés, Màrius,Kennedy, Alan R.,Aromí, Guillem,Hevia, Eva
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supporting information
p. 3247 - 3253
(2020/12/11)
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- Pd-catalyzed cross-electrophile Coupling/C-H alkylation reaction enabled by a mediator generatedviaC(sp3)-H activation
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Transition-metal-catalyzed cross-electrophile C(sp2)-(sp3) coupling and C-H alkylation reactions represent two efficient methods for the incorporation of an alkyl group into aromatic rings. Herein, we report a Pd-catalyzed cascade cross-electrophile coupling and C-H alkylation reaction of 2-iodo-alkoxylarenes with alkyl chlorides. Methoxy and benzyloxy groups, which are ubiquitous functional groups and common protecting groups, were utilized as crucial mediatorsviaprimary or secondary C(sp3)-H activation. The reaction provides an innovative and convenient access for the synthesis of alkylated phenol derivatives, which are widely found in bioactive compounds and organic functional materials.
- Jiang, Hang,Wu, Zhuo,Zhang, Yanghui
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p. 8531 - 8536
(2021/07/02)
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- Enantiomerically Enriched α-Borylzinc Reagents by Nickel-Catalyzed Carbozincation of Vinylboronic Esters
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In this paper is described a synthesis of enantiomerically enriched, configurationally stable organozinc reagents by catalytic enantioselective carbozincation of a vinylboronic ester. This process furnishes enantiomerically enriched α-borylzinc intermediates that are shown to undergo stereospecific reactions, producing enantioenriched secondary boronic ester products. The properties of the intermediate α-borylzinc reagent are probed and the synthetic utility of the products is demonstrated by application to the synthesis of (-)-aphanorphine and (-)-enterolactone.
- Chen, Jingjia,Hu, Weipeng,Jin, Jing,Lovinger, Gabriel J.,Morken, James P.,Zhang, Chenlong
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p. 14189 - 14195
(2021/09/11)
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- Mechanical metal activation for Ni-catalyzed, Mn-mediated cross-electrophile coupling between aryl and alkyl bromides
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Liquid-assisted grinding has been successfully applied to eliminate the requirements of chemical activators and anhydrous solvents in nickel-catalyzed, manganese-mediated cross-electrophile coupling between aryl and alkyl bromides. In addition to the traditional reaction parameters, mechanical ones,e.g.the rotational speed of mill, the filling degree of jar and ball size, have been found to affect the catalytic efficiency remarkably, implying the involvement of the regeneration of nickel(0) species in the rate-determining steps. A combined evaluation of the reaction and mechanical parameters led to an optimal condition under which a variety ofn-alky aromatics with various functional groups could be readily obtained in good yields with a 1 mol% catalyst loading. The practical application of liquid-assisted grinding-enabled aryl/alkyl cross-electrophile coupling has been demonstrated in the gram-scale synthesis of 6-methoxytetralone.
- Wu, Sisi,Shi, Weijia,Zou, Gang
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supporting information
p. 11269 - 11274
(2021/07/02)
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- Identification of a Surprising Boronic Acid Homocoupling Process in Suzuki-Miyaura Cross-Coupling Reactions Utilizing a Hindered Fluorinated Arene
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The Suzuki-Miyaura cross-coupling reaction of 2-bromo-1,3-bis(trifluoromethyl)benzene with arylboronic acids was evaluated and determined to suffer from the formation of large amounts of boronic acid homocoupling products in conjunction with dehalogenation. Homocoupling product formation in this process likely occurs through a rare protonolysis/second transmetalation event rather than by the well-established mechanism requiring the involvement of O 2. The scope of this boronic acid homocoupling reaction was investigated and shown to predominate with electron-deficient arylboronic acids. Finally, a good yield of cross-coupling products could be obtained by employing dicyclohexyl(2′,6′-dimethoxybiphenyl-2-yl)phosphine (SPhos) as the ligand.
- Gargaro, Samantha L.,Dunson, Bre'Shon,Sieber, Joshua D.
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supporting information
p. 511 - 516
(2020/09/21)
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- 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
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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.
- Hanafiah, Marlia M.,Lakkaboyana, Sivarama Krishna,Lakshmidevi, Jangam,Marella, Ravi Kumar,Naidu, Bandameeda Ramesh,Prasad, Sana Siva,Venkateswarlu, Katta
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- Sustainable Synthesis of Biaryls Using Silica Supported Ferrocene Appended N-Heterocyclic Carbene-Palladium Complex
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Abstract: A novel silica supported ferrocene appended N-heterocyclic carbene-palladium complex (SilFemBenzNHC@Pd) has been prepared and characterized by using fourier transform infrared (FT-IR), fourier transform Raman (FT-Raman), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and energy dispersive X-ray analysis (EDX). This novel complex served as a robust heterogeneous catalyst for the synthesis of biaryls via homocoupling of aryl boronic acids under base-free conditions in water. Recyclability experiments were executed successfully for six successive runs. Graphic Abstract: [Figure not available: see fulltext.]
- Khanapure, Sharanabasappa,Pore, Dattaprasad,Jagadale, Megha,Patil, Vaishali,Rashinkar, Gajanan
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p. 2237 - 2249
(2021/01/11)
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- A Bio-Inspired Magnetically Recoverable Palladium Nanocatalyst for the Ullmann Coupling reaction of Aryl halides and Arylboronic acids In Aqueous Media
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Palladium nanoparticles supported on polydopamine-coated iron oxide nanoparticles (Pd/Fe3O4@PDA) were found to catalyze the Ullmann homocoupling of a wide variety of aryl halides, arylboronic acids and aryldiazonium salts in aqueous media in the presence of randomly methylated β-cyclodextrin (RM-β-CD). The synthesized nanoparticles were characterized by techniques such as TEM, SEM, EDX, XPS, ICP-AES and XRD. The synthesized catalyst can be easily recovered magnetically and reused up to five cycles without any significant loss of activity. This is the first report demonstrating the use of magnetically recoverable catalyst for Ullmann homocoupling reactions of aryl halides, arylboronic acids and aryldiazonium salts in water.
- Dubey, Abhishek V.,Kumar, A. Vijay
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- Metal-free synthesis of biarenes via photoextrusion in di(tri)aryl phosphates
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A metal-free route for the synthesis of biarenes has been developed. The approach is based on the photoextrusion of a phosphate moiety occurring upon irradiation of biaryl- A nd triaryl phosphates. The reaction involves an exciplex as the intermediate and it is especially suitable for the preparation of electron-rich biarenes.
- Qrareya, Hisham,Meazza, Lorenzo,Protti, Stefano,Fagnoni, Maurizio
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supporting information
p. 3008 - 3014
(2021/01/18)
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- Kinetically Controlled Reticular Assembly of a Chemically Stable Mesoporous Ni(II)-Pyrazolate Metal-Organic Framework
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The application scope of metal-organic frameworks (MOFs) is severely restricted by their weak chemical stability and limited pore size. A robust MOF with large mesopores is highly desired, yet poses a great synthetic challenge. Herein, two chemically stable Ni(II)-pyrazolate MOFs, BUT-32 and -33, were constructed from a conformation-matched elongated pyrazolate ligand through the isoreticular expansion. The two MOFs share the same sodalite-type net, but have different pore sizes due to the network interpenetration in BUT-32. Controlled syntheses of the two MOFs have been achieved through precisely tuning reaction conditions, where the microporous BUT-32 was demonstrated to be a thermodynamically stable product while the mesoporous BUT-33 is kinetically favored. To date, BUT-32 represents the first example of Ni4-pyrazolate MOF whose structure was unambiguously determined by single-crystal X-ray diffraction. Interestingly, the kinetic product BUT-33 integrates 2.6 nm large mesopores with accessible Ni(II) active sites and remarkable chemical stability even in 4 M NaOH aqueous solution and 1 M Grignard reagent. This MOF thus demonstrated an excellent catalytic performance in carbon-carbon coupling reactions, superior to other Ni(II)-MOFs including BUT-32. These findings highlight the importance of kinetic control in the reticular synthesis of mesoporous MOFs, as well as their superiority in heterogeneous catalysis.
- He, Tao,Huang, Zhehao,Yuan, Shuai,Lv, Xiu-Liang,Kong, Xiang-Jing,Zou, Xiaodong,Zhou, Hong-Cai,Li, Jian-Rong
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supporting information
p. 13491 - 13499
(2020/09/02)
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- GEM-DISUBSTITUTED PYRROLIDINES, PIPERAZINES, AND DIAZEPANES, AND COMPOSITIONS AND METHODS OF MAKING THE SAME
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Described here are transition metal-catalyzed enantioselective arylation and vinylation reactions of α-substituted lactams, such as γ-lactams. The use of various electrophiles and ligands are described, and result in the construction of α-quaternary centers in good yields (up to 91% yield) and high enantioselectivities (up to 97% ee).
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-
Paragraph 0639-0640
(2020/07/14)
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- Efficient Pd-catalyzed oxidative homocoupling of arylboronic acids in aqueous NaClO
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An efficient, mild and practical method was developed for the synthesis of biaryls via the Pd-catalyzed oxidative homocoupling of aromatic/heteroaromatic boronic acids in aqueous NaClO.
- Li, Min-Xin,Tang, Yan-Ling,Gao, Hui,Mao, Ze-Wei
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supporting information
(2020/03/04)
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- Green-Synthesized Nickel Nanoparticles on Reduced Graphene Oxide as an Active and Selective Catalyst for Suzuki and Glaser-Hay Coupling Reactions
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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.
- Murugan, Karthik,Nainamalai, Devarajan,Kanagaraj, Pavithara,Nagappan, Saravana Ganesan,Palaniswamy, Suresh
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- Aerobic and Ligand-Free Manganese-Catalyzed Homocoupling of Arenes or Aryl Halides via in Situ Formation of Aryllithiums
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Ligand-free manganese-catalyzed homocoupling of arenes or aryl halides can be carried out under aerobic conditions via the in situ formation of the corresponding aryllithiums. A wide range of biaryls and derivatives has been obtained, and a mechanism involving monomeric manganese-oxo complexes has been proposed on the basis of DFT calculations.
- Liu, Yujia,Bergès, Julien,Zaid, Yassir,Chahdi, Fouad Ouazzani,Van Der Lee, Arie,Harakat, Dominique,Clot, Eric,Jaroschik, Florian,Taillefer, Marc
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p. 4413 - 4420
(2019/03/26)
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- PdAu alloy nanoparticles supported on nitrogen-doped carbon black as highly active catalysts for Ullmann coupling and nitrophenol hydrogenation reactions
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Noble metal-based catalysts have been proven to be active for catalytic organic reactions. The selectivity and conversion can be improved by integration with proper carrier materials, and further modulated by tuning the composition as well as the electronic structure of the active noble metals. Compared with unsupported monometallic catalysts, the synergistic interactions between neighboring metals and the combined effects between the carrier materials and the active components often give rise to positive influences on the enhancement of the catalytic efficiency and selectivity. In this work, we report a facile process for the fabrication of nitrogen-doped carbon black (NCB) supported PdAu bimetallic nanoparticles (NPs) with a uniform dispersion and narrow size distribution. The PdAu/NCB catalyst with a Pd/Au mole ratio of 1/1 shows the highest activity towards both Ullmann coupling reactions of aryl halides and the hydrogenation reaction of nitrophenols. Moreover, this bimetallic catalyst also exhibits a superior recycling durability to that of monometallic Pd/NCB and Au/NCB catalysts. The enhanced catalytic performance of the bimetallic catalyst is mainly due to the large BET specific surface area (125.45 m2 g-1) and the synergy between the individual components of the catalyst.
- Han, Fengyan,Xia, Jiawei,Zhang, Xinglong,Fu, Yongsheng
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p. 17812 - 17823
(2019/06/24)
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- Ligand's electronegativity controls the sense of enantioselectivity in BIFOP-X palladium-catalyzed allylic alkylations
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Palladium-catalyzed allylic alkylations of sodium dimethyl malonate with 1,3-diphenylallyl acetate, employing BIFOP-H (biphenylbisfencholphosphite) and analogue (i.e. BIFOP-X, X = D, Cl, CN, N3) ligands, all yield (S)-enantiomeric products, while alkylations to cyclohexenyl acetate yield the (R)-enantiomeric C-C coupling product (up to 91% yield, 70% ee). The fluoro derivative BIFOP-F however, "switches" the sense of enantioselectivity, yielding the (R)-enantiomer for 1,3-diphenylallyl acetate and the (S)-enantiomer for the cyclohexenyl acetate (up to 92% yield, 67% ee). Computational analyses of transition structures (M06-2X-D3/def2-TZVP//B3LYP-D3(BJ)/def2-SVP) for these Pd-catalyzed allylic alkylations reproduce the experimental preference of BIFOP-H (and analogue BIFOP-X ligands) for (R)- or (S)-enantiomeric products of 1,3-diphenylallyl or cyclohexenyl acetate, respectively. The "F-switch" of the sense of enantioselectivity from BIFOP-H to BIFOP-F is also apparent computationally and is found (NBO-analyses) to originate from lp(Pd) → σ?(P-O) or lp(Pd) → σ?(P-F) hyperconjugations. The higher electronegativity of F vs. H in BIFOP-X hence controls the sense of enantioselectivity of this Pd-catalyzed allylic alkylation.
- Brüllingen, Eric,Neud?rfl, J?rg-Martin,Goldfuss, Bernd
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supporting information
p. 15743 - 15753
(2019/10/19)
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- Ni-Catalyzed Reductive Cyanation of Aryl Halides and Phenol Derivatives via Transnitrilation
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Herein, we report a Ni-catalyzed reductive coupling for the synthesis of benzonitriles from aryl (pseudo)halides and an electrophilic cyanating reagent, 2-methyl-2-phenyl malononitrile (MPMN). MPMN is a bench-stable, carbon-bound electrophilic CN reagent that does not release cyanide under the reaction conditions. A variety of medicinally relevant benzonitriles can be made in good yields. Addition of NaBr to the reaction mixture allows for the use of more challenging aryl electrophiles such as aryl chlorides, tosylates, and triflates. Mechanistic investigations suggest that NaBr plays a role in facilitating oxidative addition with these substrates.
- Mills, L. Reginald,Graham, Joshua M.,Patel, Purvish,Rousseaux, Sophie A. L.
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supporting information
p. 19257 - 19262
(2019/12/02)
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- Aerobic Homocoupling of Arylboronic Acids Catalyzed by Regenerable Pd(II)@MIL-88B-NH2(Cr)
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A fast and operationally simple method for the aerobic homocoupling of arylboronic acids is described. The process is catalyzed by Pd(II) complexes supported on the metal-organic framework MIL-88B-NH2(Cr). The benefits of this approach include the use of a benign oxidant/solvent mixture at room temperature with catalytic amounts of base, easy recovery of the catalyst, and easy isolation of the products. Very high conversions and good yields were achieved for a variety of substrates, and the process was also carried out on a larger scale with the same efficiency. The catalyst was found to suffer deactivation due to progressive reduction and agglomeration of palladium into inactive metal clusters/particles. An innovative procedure for the oxidative redispersion and regeneration of the active Pd(II)@MOF species is presented.
- Valiente, Alejandro,Carrasco, Sergio,Sanz-Marco, Amparo,Tai, Cheuk-Wai,Bermejo Gómez, Antonio,Martín-Matute, Belén
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p. 3933 - 3940
(2019/05/22)
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- The first report on the transition metal-free homocoupling of aryl halides in the presence of l-cysteine
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A green and efficient methodology for the coupling of aryl halides without the addition of a transition metal catalyst has been presented. The biaryl coupling of haloarenes can be promoted by l-cysteine and potassium hydroxide. This is the first report on the synthesis of symmetrical biaryls under transition metal-free conditions.
- Ghorbani-Choghamarani, Arash,Taherinia, Zahra
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supporting information
p. 10989 - 10992
(2018/07/05)
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- The β-cyclodextrin decorated with palladium nanoparticles without pretreatment: An efficient heterogeneous catalyst for biaryls synthesis
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β-Cyclodextrin decorated with palladium nanoparticles (PdNPs@β-CD) without pretreatment led to a suitable catalyst for the biaryls synthesis in water. A simple and straightforward method was developed for the preparation of PdNPs@β-CD as a green catalyst. The prepared catalyst was characterized by Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), atomic absorption spectroscopy (AAS), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDS) measurements. It was found that PdNPs@β-CD exhibits high performance in Ullmann, Suzuki and Hiyama coupling reactions.
- Feiz, Afsaneh,Loni, Masood,Naderi, Soheila,Bazgir, Ayoob
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- WEPA: a bio-derived medium for added base, π-acid and ligand free Ullmann coupling of aryl halides using Pd(OAc)2
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A bio-derived sustainable medium based on water extract of pomegranate ash (WEPA) has, for the first time, been developed for the homocoupling of aryl halides under palladium-assistance. Avoiding the requirement of an external base, ligand and π-acid, the use of the proposed renewable medium offers remarkable attributes like wide substrate scope, good to nearly quantitative yields of biphenyls with exceptional chemoselectivity and scale up viability.
- Lakshmidevi, Jangam,Appa, Rama Moorthy,Naidu, Bandameeda Ramesh,Prasad, S. Siva,Sarma, Loka Subramanyam,Venkateswarlu, Katta
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supporting information
p. 12333 - 12336
(2018/11/30)
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- Dimerization of Aromatic Compounds Using Palladium-Carbon-Catalyzed Suzuki-Miyaura Cross-Coupling by One-Pot Synthesis
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The aromatic dimers play a significant role in many aspects. Herein, we report a simple palladium-carbon catalyst that is highly effective for the dimerization of brominated aromatic compounds under mild conditions using abundant brominated aromatic compounds, bis(pinacolate)diboron and potassium acetate by a 'one-pot' method. This process, which we believe proceeds via a Suzuki-Miyaura cross-coupling reaction mechanism, allows access to a variety of aromatic compounds under mild reaction conditions and has a good functional group tolerance with moderate to high yields.
- Du, Fangyu,Zhou, Qifan,Liu, Dongdong,Fang, Ting,Shi, Yajie,Du, Yang,Chen, Guoliang
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supporting information
p. 779 - 784
(2018/02/09)
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- Palladium Catalyzed C-I and Vicinal C-H Dual Activation of Diaryliodonium Salts for Diarylations: Synthesis of Triphenylenes
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Using the synthetic strategy of palladium-catalyzed dual activation of both C-I and vicinal C-H bonds of diaryliodonium salts, we report an approach for direct diarylations of 2-bromobiphenyls or bromobenzenes. As a result, a wide range of triphenylenes with various substituents have been synthesized in good yields. These triphenylenes are expected to be employed in the "bottom-up" synthesis of functional aromatic molecules in material science.
- Wu, Xunshen,Han, Jianwei,Wang, Limin
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- Fast, Efficient and Low E-Factor One-Pot Palladium-Catalyzed Cross-Coupling of (Hetero)Arenes
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The homocoupling of aryl halides and the heterocoupling of aryl halides with either aryl bromides or arenes bearing an ortho-lithiation directing group are presented. The use of a Pd catalyst, in combination with t-BuLi, allows for the rapid and efficient formation of a wide range of polyaromatic compounds in a one pot procedure bypassing the need for the separate preformation of an organometallic coupling partner. These polyaromatic structures are obtained in high yields, in 10 min at room temperature, with minimal waste generation (E-factors as low as 1.5) and without the need for strict inert conditions, making this process highly efficient and practical in comparison to classical methods. As illustration, several key intermediates of widely used BINOL-derived structures are readily prepared.
- Pinxterhuis, Erik B.,Visser, Paco,Esser, Iwan,Gualtierotti, Jean-Baptiste,Feringa, Ben L.
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supporting information
p. 9452 - 9455
(2017/10/23)
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- Synthesis, Characterization, and Phytotoxic and Antifungal Activities of Biphenyl Derivatives
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Three series of biphenyl derivatives are synthesized, characterized and evaluated for Lemna minor phytotoxicity and antifungal activity. The synthetic biphenyl analogues 2c and 6c demonstrate significant activity, while compounds 4b and 6b demonstrate hig
- Ali,Irshad,Asghar
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p. 2177 - 2182
(2018/12/11)
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- Palladium (II)-Catalyzed Decarboxylative Cross-Dehydrogenative Coupling: Direct Synthesis of meta-Substituted Biaryls from Aromatic Acids
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A palladium-catalyzed tandem process of simple aromatic acids has been achieved to afford meta-substituted biaryls in moderate to good yields. The reaction proceeds via carboxyl-directed intermolecular cross-dehydrogenative coupling and subsequent decarboxylation. The new C?C bonds in this transformation are formed in the ortho position of carboxyl and the reaction tolerates electron-rich acids. Both symmetrical and unsymmetrical meta-substituted biaryls can be directly synthesized via this method. (Figure presented.).
- Pu, Fan,Zhang, Lin-Yan,Liu, Zhong-Wen,Shi, Xian-Ying
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supporting information
p. 2644 - 2649
(2018/07/29)
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- A Copper-Catalyzed Reductive Defluorination of β-Trifluoromethylated Enones via Oxidative Homocoupling of Grignard Reagents
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An efficient copper-catalyzed reductive defluorination of β-trifluoromethylated enones via an oxidative homocoupling of Grignard reagents is reported. The reaction proceeded smoothly with a wide range of substrates, including the ones bearing aromatic heterocycles, such as furyl and thienyl ring systems in high yields (80-92%, except one example) under mild conditions. This provides a practical method for synthesis of gem-difluoroolefin ketones. It is also worth noting that this homocoupling process of Grignard reagents using β-trifluoromethylated enones as oxidizing reagents is effective for both the Csp2-Csp2 and Csp3-Csp3 bond formations, including for substrates whose β-hydride elimination of the corresponding transition metal alkyl complex is particularly facile, affording coupling products with high yields (83-95%), simultaneously.
- Wu, Xiaoting,Xie, Fang,Gridnev, Ilya D.,Zhang, Wanbin
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p. 1638 - 1642
(2018/03/23)
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- Iron-Catalyzed Isopropylation of Electron-Deficient Aryl and Heteroaryl Chlorides
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Traditional methods for the preparation of secondary alkyl-substituted aryl and heteroaryl chlorides challenge both selectivity and functional group tolerance. This contribution describes the use of statistical design of experiments to develop an effective procedure for the preparation of isopropyl-substituted (hetero)arenes with minimal isopropyl to n-propyl isomerization. The reaction tolerates electronically diverse aryl chloride coupling partners, with excellent conversion observed for strongly electron-deficient aromatic rings, such as esters and amides. Electron-rich systems, including methyl- and methoxy-substituted aryl chlorides, were found to be less reactive. Furthermore, the reaction was found to be most successful when heteroaryl chlorides were submitted to the cross-coupling protocol. By mapping substituent effects on reaction selectivity, we were able to show that electron-deficient aryl chlorides are essential for efficient coupling, and use electronic structure calculations to predict the likelihood of successful coupling through the estimation of the electron affinity of each aryl chloride. Moderate isolated yields were achieved with selected aryl chlorides, and moderate to good isolated yields were obtained for all the heteroaryl chlorides coupled. Excellent selectivity was observed when a 2,6-dichloroquinoline was used, allowing mono-substitution on a challenging substrate. (Figure presented.).
- Sanderson, James N.,Dominey, Andrew P.,Percy, Jonathan M.
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p. 1007 - 1017
(2017/03/27)
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- A method for synthesis of biphenyl derivatives (by machine translation)
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The invention discloses a biphenyl derivative synthesis method, the method to transition metal palladium as the catalyst, through the aromatic carboxylic acid carboxyl group between the ortho position of the cross-dehydrogenation coupling, decarboxylation reaction, one-step simple, efficient synthesized a series of biphenyl derivatives. Raw materials of the invention is simple and easy, simple operation, environment-friendly and the like. (by machine translation)
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Paragraph 0014-0020; 0028-0034
(2017/12/05)
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- Bimetallic Au-Pd nanochain networks: Facile synthesis and promising application in biaryl synthesis
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A simple and facile method is described for the morphology-controlled synthesis of bimetallic Au-Pd alloyed nanochain networks (NNCs) that show high catalytic performance for the Ullmann intermolecular homocoupling of aromatic or alkyl halides (X = I, Br, Cl) in aqueous media and can be reused at least five times, which can also be applied to intramolecular homocoupling.
- Wang, Zheng-Jun,Wang, Xia,Lv, Jing-Jing,Feng, Jiu-Ju,Xu, Xinhua,Wang, Ai-Jun,Liang, Zhiwu
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p. 3894 - 3899
(2017/07/12)
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- Reductive Homocoupling of Organohalides Using Nickel(II) Chloride and Samarium Metal
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A homocoupling method for organohalides and organosulfonates promoted by samarium metal and HMPA, and catalyzed by NiCl2 has been developed. Various organohalides (benzyl, aryl, heterocyclic, alkenyl and alkyl halides), α-haloacetophenones, and phenyl organosulfonates were tolerated, and the reaction afforded coupling products with high efficiency. Excellent chemoselectivity was exhibited between halides and other groups, such as ?COOH, ?NO2, halogen, heterocyclic ring, ester, and ketone groups. The stereoselectivity suggested that the reaction mechanism might involve an organosamarium species.
- Liu, Yongjun,Xiao, Shuhuan,Qi, Yan,Du, Feng
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p. 673 - 678
(2017/03/22)
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- Carbon-carbon bond forming reactions via Pd-catalyzed detellurative homocoupling of diorganyl tellurides
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A simple and highly efficient method for the constructions of Csp-Csp, Csp2-Csp2 and Csp3-Csp3 bonds is reported. The symmetrical diaryl tellurides undergo detellurative homocouplings to afford symmetrical biaryl products. The reactions are carried out at ambient temperature using PdCl2 as a catalyst in the presence of Ag2O and Na2CO3. Similarly, the detellurative homocouplings of dibenzyl telluride and bis(phenylethynyl)telluride give bibenzyl and the conjugated diyne, respectively.
- Zhang, Shaozhong,Kolluru, Lalitha,Vedula, Souseelya K.,Whippie, Drew,Jin, Jin
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p. 3594 - 3597
(2017/08/23)
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- Oxidative homocoupling reaction of aryltrimethylsilanes by Pd/o-chloranil catalysis
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A practical oxidative homocoupling reaction of aryltri-methylsilanes has been achieved by Pd/o-chloranil catalytic system. The reaction shows the good functional group tolerability toward bromo, fluoro, ester, and methoxy groups to give a series of biaryls bearing electron-withdrawing and -donating groups. The boronate group is also retained on biaryls without any ArB bond cleavage, which is highly advantageous for orthogonal coupling.
- Shibata, Mari,Ito, Hideto,Itami, Kenichiro
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supporting information
p. 1701 - 1704
(2017/11/23)
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- Direct ortho Arylation of Anisoles via the Formation of Four-Membered Lithiumcycles/Palladacycles
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We report here our latest discovery on the directed lithiation and palladium-catalyzed arylation of anisoles. During this research, the formation of a four-membered lithiumcycle followed by transmetalation to the corresponding palladacycle has been achieved, which is difficult to be obtained from palladium-catalyzed C-H activation processes. This approach has provided an alternative way of introducing functionalities to arenes such as anisoles, thioanisoles, and anilines. This approach also features an excellent monoselectivity compared with reactions under transition-metal-catalyzed conditions.
- Xiong, Xiaoyu,Zhu, Ranran,Huang, Lin,Chang, Shuqin,Huang, Jianhui
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supporting information
p. 2046 - 2050
(2017/09/13)
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- Spatially isolated palladium in porous organic polymers by direct knitting for versatile organic transformations
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We report here a direct knitting Method for preparation of highly robust, effective while air- and moisture-tolerant, and readily recyclable three-dimensional (3D) porous polymer-Pd network (PPPd) from the widely used Pd(PPh3)4. Electro-beam induced Pd atom crystallization was observed for the first time in organic polymer and revealed the ultrafine dispersion of palladium atoms. Challenging types of Suzuki-Miyaura couplings, reductive coupling of aryl halides and oxidative coupling of arylboronic acid were successively catalyzed by PPPd in aqueous media. Also catalytically selective C–H functionalization reactions were achieved with orders of magnitude more efficient than conventional Pd homogeneous catalysts. The strategy developed here provides a practical method for easy-to-make yet highly efficient heterogeneous catalysis.
- Wang, Xinbo,Min, Shixiong,Das, Swapan K.,Fan, Wei,Huang, Kuo-Wei,Lai, Zhiping
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p. 101 - 109
(2017/10/06)
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- With catalytic 3 - methoxybenzene boronic acid of the anthracycline double-triazole - novel scaling copper complex and its preparation method
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The invention discloses a preparation method of {[Cu(tatrz)2(H2O)2](BF4)2} (1) (tatrz=1-[9-(1H-1,2,4-triazol-1-yl)anthracen-10-yl]-1H-1,2,4-triazole) and a potential application value thereof in the catalysis of coupling reaction of 3-methoxy phenylboronic acid. According to the method, a normal-temperature volatilization method is adopted, namely the complex is prepared from Cu(BF4)2 and tatrz under the conditions of stirring and volatilizing at normal temperature. The invention further discloses application of {[Cu(tatrz)2(H2O)2](BF4)2} (1) (tatrz=1-[9-(1H-1,2,4-triazol-1-yl)anthracen-10-yl]-1H-1,2,4-triazole) as a coupling reaction catalyst of 3-methoxy phenylboronic acid.
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Paragraph 0043; 0047; 0048
(2017/04/28)
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- With catalytic 3 - methoxybenzene boronic acid oxygen ether double-triazole copper complex and its preparation method
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The invention discloses a preparation method for [Cu(L)2(NO3)2] (1) (L=1-(4-(4-(1H-1, 2, 4-triazole-1-yl)phenoxy)phenyl)-1H-1, 2, 4-triazole) and potential application value of the complex in catalyzing coupling reaction of 3-methoxyphenylboronic acid. The method employs a ''normal temperature volatilization process'', i.e. normal temperature stirring volatilization of Cu(NO3)2 and L to prepare the complex. The invention further discloses application of [Cu(L)2(NO3)2] (1) (L=1-(4-(4-(1H-1, 2, 4-triazole-1-yl)phenoxy)phenyl)-1H-1, 2, 4-triazole) as a coupling reaction catalyst for 3-methoxyphenylboronic acid.
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Paragraph 0042; 0046-0047
(2017/05/26)
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- Three-dimensional manganese formate dehydrate complex single crystal and application
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The invention discloses a three-dimensional manganese formate dehydrate complex single crystal, as well as a preparation method and an application thereof. The structure of the complex single crystal is [Mn (COO) 3].2H2O. Meanwhile, the invention also discloses the preparation method of the single crystal. A room-temperature volatilization method is adopted, that is, MnC12.4H2O and formic acid are stirred in water for half an hour, and then filtered, and after filtrate is volatilized for two weeks, a colorless bulk crystal suitable for X-ray single-crystal diffraction is obtained, wherein the molar ratio of formic acid to MnC12.4H2O is 1 to 1. The invention further discloses the application of specificity of the three-dimensional manganese formate dehydrate complex single crystal as a catalyst in generation of 4, 4'-difluorobiphenyl from fluorophenylboronic acid.
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Paragraph 0014; 0016
(2017/02/28)
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- 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) cadmium mixed-ligand complex single crystal and application
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The invention discloses a 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) hydroxyisophthalic acid cadmium complex single crystal and a preparation method and application thereof. A structure is [Cd(L)(hipa)] DMF, wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazole-1-yl)phenyl)-1H-1,2,4-triazole; hipa=hydroxyisophthalic acid; DMF=N,N'-dimethyl formamide. The invention also discloses the preparation method of the single crystal. The preparation method is a normal-temperature volatilizing method, comprising the following steps of stirring L, hipa and Cd(NO3)2 6H2O in a mixed solvent of water and DMF for 0.5h, filtering, and volatilizing a filtrate for two weeks at the normal temperature, so as to obtain the colorless blocky crystal which is suitable for X-ray single crystal diffraction, wherein the molar ratio of L:hipa:Cd(NO3)2 6H2O is 1:1:1. The invention further discloses the application of the 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) hydroxyisophthalic acid cadmium complex single crystal special for fluorophenylboronic acid to generate a 4,4'-difluorobiphenyl catalyst.
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Paragraph 0018
(2017/04/07)
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- 1,4-dimethyl-2,5-bis-1H-1,2,4-double-triazole zinc mixed complex single crystal and application thereof
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The invention discloses a 1,4-dimethyl-2,5-bis-1H-1,2,4-double-triazole meta-hydroxyl isophthalic acid zinc complex single crystal as well as a preparation method and application thereof. The structure of the single crystal is as follows: [Zn(L)(hipa)].DMAC.2H2O, wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazole-1-yl)phenyl)-1H-1,2,4-triazole; hipa=meta-hydroxyl isophthalic acid; DMAC=N,N'-dimethylacetamide. The invention also discloses the preparation method of the single crystal. The preparation method adopts a room temperature volatilization method, specifically, comprises the steps of adding the L, the hipa and Zn(NO3)2.6H2O into a mixed solvent of water and the DMAC, stirring for half an hour, and then filtering; volatilizing filtrate at room temperature for two weeks to obtain a colorless bulk crystal suitable for X-ray single crystal diffraction, wherein the molar ratio of the L to the hipa to the Zn(NO3)2.6H2O is equal to 1:1:1. The invention further discloses the application of specificity of the 1,4-dimethyl-2,5-bis-1H-1,2,4-double-triazole meta-hydroxyl isophthalic acid zinc complex single crystal in the aspect of a catalyst for generating 4,4'-difluorobiphenyl by using p-fluorophenyl boronic acid.
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Paragraph 0018
(2017/04/07)
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- 1,4-dimethyl-2,5-bis-1H-double-triazole pyromellitic acid copper complex single crystal and application thereof
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The invention discloses a 1,4-dimethyl-2,5-bis-1H-double-triazole pyromellitic acid copper complex single crystal as well as a preparation method and application thereof. The structure of the single crystal is as follows: [Cu(L)(pma)], wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazole-1-yl)phenyl)-1H-1,2,4-triazole; pma=pyromellitic acid. The invention also discloses the preparation method of the single crystal. The preparation method adopts a room temperature volatilization method, specifically, comprises the steps of adding the L, the pma and Cu(NO3)2.6H2O into water, stirring for half an hour, and then filtering; volatilizing filtrate at room temperature for two weeks to obtain a purple bulk crystal suitable for X-ray single crystal diffraction, wherein the molar ratio of the L to the pma to the Cu(NO3)2.6H2O is equal to 1:1:1. The invention further discloses the application of specificity of the 1,4-dimethyl-2,5-bis-1H-double-triazole pyromellitic acid copper complex single crystal in the aspect of a catalyst for generating 4,4'-difluorobiphenyl by using p-fluorophenyl boronic acid.
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Paragraph 0016-0019
(2017/04/11)
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- 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) terephthalic acid copper complex single crystal and application
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The invention discloses a 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) terephthalic acid copper complex single crystal and a preparation method and application thereof. A structure is [Cu(L)(tpa)(H2O)], wherein L=1-(2,5-dimethyl-4-(1H-1,2,4-triazole-1-yl)phenyl)-1H-1,2,4-triazole; tpa=terephthalic acid. The invention also discloses the preparation method of the single crystal. The preparation method is a normal-temperature volatilizing method, comprising the following steps of stirring L, tpa and Cu(NO3)2 6H2O in water for 0.5h, filtering, and volatilizing a filtrate for two weeks at the normal temperature, so as to obtain the blue blocky crystal which is suitable for X-ray single crystal diffraction, wherein the molar ratio of L:tpa:Cu(NO3) 6H2O is 1:1:1. The invention further discloses the application of the 1,4-dimethyl-2,5-di-1H-1,2,4-bis (triazol 1 yl) terephthalic acid copper complex single crystal special for fluorophenylboronic acid to generate a 4,4'-difluorobiphenyl catalyst.
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Paragraph 0016; 0019; 0020
(2017/04/08)
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- Aryl Ketones as Single-Electron-Transfer Photoredox Catalysts in the Nickel-Catalyzed Homocoupling of Aryl Halides
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An intriguing photoredox system for the homocoupling of aryl halides is reported wherein thioxanthone catalyzes a single-electron transfer from an amine reductant to nickel.
- Masuda, Yusuke,Ishida, Naoki,Murakami, Masahiro
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supporting information
p. 5822 - 5825
(2016/12/18)
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- Cobalt-Catalyzed Oxidative Homocoupling of Arylzinc Species
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A novel procedure for the synthesis of functionalized symmetrical biaryl compounds is described. The reaction proceeds via the oxidative homocoupling of arylzinc species formed by cobalt catalysis in the presence of air or p-benzoquinone depending on the nature of the functional group.
- Bourne-Branchu, Yann,Moncomble, Aurélien,Corpet, Martin,Danoun, Gregory,Gosmini, Corinne
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p. 3352 - 3356
(2016/09/12)
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- Ligand- and Base-Free Access to Diverse Biaryls by the Reductive Coupling of Diaryliodonium Salts
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A ligand- and base-free, Pd-catalyzed protocol to access a wide range of symmetrical and unsymmetrical biaryls from stable diaryliodonium salts was developed. The reaction involved the use of an effective and recyclable Pd/polyethylene glycol-400 catalyst system to harness the aryl moieties of two diaryliodonium salts; the ensuing biaryls may be utilized to synthesize an array of useful compounds, including 5-aryluracils, carbazoles, chromenones, fluorenones, phenathridines, and boscalid analogues.
- Arun,Reddy, P. O. Venkataramana,Pilania, Meenakshi,Kumar, Dalip
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supporting information
p. 2096 - 2100
(2016/05/09)
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- Transition-Metal-Free Cross-Coupling of Aryl Halides with Arylstannanes
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Transition-metal-free LiCl-promoted cross-coupling reactions of tetraphenyltin, trichlorophenyl-, dichlorodiphenyl-, and chlorotriphenylstannanes with aryl halides in DMF provided access to biaryls in good to high yields. Up to four phenyl groups were transferred from the organostannanes substrates. The aryls bearing electron-withdrawing groups in either halides or organotin substrates gave coupling products in higher yields. The methodology has been applied for the efficient synthesis of ipriflavones.
- He, Qing,Wang, Liwen,Liang, Yong,Zhang, Zunting,Wnuk, Stanislaw F.
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p. 9422 - 9427
(2016/10/17)
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