- Ferrocenylated imine- and amine(secondary/tertiary)- phosphine P^N ligands and their Pd(II) complexes: Synthesis and structural characterization
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A new family of ferrocenylated P^N ligands where the nitrogen donor is either of an imine or amine (secondary/tertiary), was synthesized. The condensation reaction between diphenylphosphino propylamine and formyl ferrocene led to the formation of imine ligand [(η5-C5H5)Fe{(η5-C5H4)CH=N-(CH2)3-PPh2)}] (1), which on reduction with NaBH4 gave secondary amine ligand [(η5-C5H5)Fe{(η5-C5H4)CH2-NH-(CH2)3-PPh2)}] (2). Additionally, nucleophilic substitution reaction of diphenylphosphino ethyl/propyl amine with [FcCH2NMe3+][I?] salt leads to tertiary-amine ligand [(η5-C5H5)Fe(η5-C5H4)CH2]2-N-(R-PPh2) where R= C2H4 (3) and C3H6 (4). The newly synthesized ferrocenylated ligands were then complexed with Pd(II) giving [cis(κ2-P^N)PdCl2] type complexes (5-8), where imine, secondary amine, and tertiary amine ligands act as a bidentate ligand. The molecular structures of ligand (3), and complexes (5), (6), and (7) have also been determined by X-ray crystallography. In the molecular structures of these complexes, the Pd(II) center presents a distorted square-planar geometry. During the isolation of ligand (4), corresponding phosphine oxide (4A) along with a phosphonium salt (4B) was also isolated as by-products and were characterized by X-ray crystallography. The preliminary catalytic evaluation of complex (7) in the Suzuki-Miyaura cross-coupling reaction of arylboronic acids with aryl bromides was performed.
- Anzaldo, Bertin,Gavi?o, Ruben,Gutiérrez, René,Sharma, Pankaj,Toscano, Alfredo R.,Villamizar C, Claudia P.
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- Ferrocene-Labeled Carbon-Encapsulated Iron Nanoparticles: The First Magnetic Nanocatalysts for C-H Arylation toward 1,1′-Biphenyl Formation
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The first magnetic nanocatalysts for C-H arylation toward 1,1′-biphenyl formation are described. The nanocatalysts are based on conjugates of ferrocene and carbon-encapsulated iron nanoparticles. The highest catalytic activity was found for ferrocene conjugated to carbon-encapsulated iron nanoparticles via the N-methylpyrrolidine moiety. In the presence of the nanocatalyst, various 1,1′-biphenyls can be obtained in high yields (84-90%). The effect of substitution of the aniline's phenyl ring on the reaction yield is also included in this work. The nanocatalyst can be easily separated from the reaction mixture and can be reused in up to four reaction cycles without any loss of its high catalytic activity. Our work sheds light on a potential application of functionalized carbon-encapsulated iron nanoparticles in modern industrial organic processes toward more economical manufacturing of organic compounds.
- Kasprzak, Artur,Bystrzejewski, Michal,Poplawska, Magdalena
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- Morphology control of nanofibril donor-acceptor heterojunction to achieve high photoconductivity: Exploration of new molecular design rule
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Donor-acceptor nanofibril composites have been fabricated, and the dependence of their photocurrent response on the structure and morphology of the donor part has been systematically investigated. The nanofibril composites were composed of template nanofibers, assembled from an electron acceptor molecule, perylene tetracarboxylic diimide (PTCDI), onto which (through drop-casting) various electron donor molecules (D1-D4) were coated. The donor molecules have the same π-conjugated core, but different side groups. Due to the different side groups, the four donor molecules showed distinctly different propensity for intermolecular aggregation, with D1-D3 forming segregated phases, while D4 prefers homogeneous molecular distribution within the film. It was found that the nanofibril composites with D4 exhibit the highest photocurrent, whereas those with aggregation-prone D1-D3 exhibited much lower photocurrent under the same illumination condition. Solvent annealing is found to further enhance the aggregation of D1-D3 but facilitate more uniform molecular distribution of D4 molecules. As a result, the photocurrent response of PTCDI fibers coated with D1-D3 decreased after vapor annealing, whereas those coated with D4 further increased. The detrimental effect of the aggregation of donor molecules on the PTCDI fiber is likely due to the enhanced local electrical field built up by the high charge density around the aggregate-nanofiber interface, which hinders the charge separation of the photogenerated electron-hole pair. The results reported in this study give further insight into the molecular structural effect on photoconductivity of hybrid materials, particularly those based on donor-acceptor composites or interfaces, and provide new molecular design rules and material processing guidelines to achieve high photoconductivity.
- Huang, Helin,Chou, Ching-En,Che, Yanke,Li, Ligui,Wang, Chen,Yang, Xiaomei,Peng, Zhonghua,Zang, Ling
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- Functionalized Phosphonium Ionic Liquids: Synthesis and Application
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A series of phosphonium salts with sterically hindered cation But3P+(CH2COOEt)X- (X = Cl, BF4, N(SO2CF3)2) (1) was prepared for the first time. Palladium nanoparticles (PdNPs) stabilized by (1) showed moderate activity as catalyst in Suzuki cross-coupling reaction of bromoarenes and phenylboronic acid.
- Arkhipova, Daria,Ermolaev, Vadim,Miluykov, Vasili,Nigmatullina, Lilia,Sinyashin, Oleg
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- METHOD FOR PRODUCING HALOGEN COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for efficiently producing an aromatic compound containing a halogen group(s). SOLUTION: Provided is a method for producing a halogen compound represented by the following general formula (1), comprising reacting an iodine compound represented by the following general formula (2) and a compound represented by the following general formula (3) in the presence of a transition metal compound, at least one phosphine compound selected from the group consisting of 1,1'-bis(diphenylphosphino)ferrocene and 4,5'-bis(diphenylphosphino)-9,9'-dimethylxanthene, and a base. (In the formula, Ar1 and Ar2 each independently represent a C1-40 organic group; X represents a bromine group, a chlorine group, a fluorine group, or a trifluoromethanesulfonate group, and when there are a plurality of X's, they may be the same or different; n represents an integer equal to or larger than 1; R's each independently represent a hydrogen atom, a C1-4 alkyl group, or a phenyl group, and two R's may be linked to form a ring containing oxygen atoms and a boron atom.) SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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Paragraph 0054-0060; 0069-0071; 0091-0093
(2021/09/29)
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- Benchtop-Stabssle Hypervalent Bromine(III) Compounds: Versatile Strategy and Platform for Air- And Moisture-Stable λ3-Bromanes
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We present the first synthesis of air/moisture-stable λ3-bromanes (9and10) by using a cyclic 1,2-benzbromoxol-3-one (BBX) strategy. X-ray crystallography and NMR and IR spectroscopy ofN-triflylimino-λ3-bromane (12) revealed that the bromine(III) center is effectively stabilized by intramolecular R-Br-O hypervalent bonding. This strategy enables the synthesis of a variety of air-, moisture-, and benchtop-stable Br-hydroxy, -acetoxy, -alkynyl, -aryl, and bis[(trifluoromethyl)sulfonyl]methylide λ3-bromane derivatives.
- Miyamoto, Kazunori,Saito, Motomichi,Tsuji, Shunsuke,Takagi, Taisei,Shiro, Motoo,Uchiyama, Masanobu,Ochiai, Masahito
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p. 9327 - 9331
(2021/07/01)
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- Palladium-catalyzed relay C–H functionalization to construct novel hybrid-arylcyclophosphorus ligand precursors
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A new relay C–H functionalization of di([1,1′-biphenyl]-2-yl)phosphine oxide to obtain esterified and hydroxylated products with different hypervalent iodines as oxidants under palladium catalysis is disclosed. This reaction provides a more effective and concise strategy for the synthesis of novel structural hybrid-arylcyclophosphorus ligand precursors with a wide range of substrates and good functional group tolerance.
- Bai, Peng-Bo,Wang, Juan,Yang, Shang-Dong
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supporting information
(2021/11/17)
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- Synthesis of Dibenzosiloles through Electrocatalytic Sila-Friedel-Crafts Reaction
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A novel electrocatalyzed method for the preparation of dibenzosiloles was developed through intramolecular C?H/Si?H dehydrogenative coupling strategy starting from biarylhydrosilanes. Both electro-donating and electro-withdrawing substitution groups were tolerated for this transformation, and the desired dibenzosilole products could be obtained in moderate to excellent yields. A sila-Friedel-Crafts reaction mechanism was proposed on the basis of previous literature and our controlled experiments. (Figure presented.).
- Han, Pan,Yin, Mengyun,Li, Haiqiong,Yi, Jundan,Jing, Linhai,Wei, Bangguo
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supporting information
p. 2757 - 2761
(2021/04/16)
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- Rh(III)-Catalyzed Annulation of 2-Biphenylboronic Acid with Diverse Activated Alkenes
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Rhodium(III)-catalyzed annulation of 2-biphenylboronic acids with three classes of activated alkenes has been realized, leading to the synthesis of fused or bridged cyclic skeletons via transmetalation-initiated C-H activation. In the annulative coupling of 2-biphenylboronic acid with a CF3-substituted enone, the bulky cyclopentadienyl ligand (CptBu) in the catalyst proved effective to promote the reductive elimination process prior to protonolysis, affording the [4 + 2] annulated products instead of the simple 1,4-addition product. Seven-membered rings were obtained when disubstituted cyclopropenones were employed. Bridged cycles were isolated from the coupling of 2-biphenylboronic acid with benzoquinones as a result of 2-fold Michael additions. The substrate scopes were found to be broad with up to 99% yield under air-tolerant conditions.
- Chang, Junbiao,Dong, Zhenzhen,Li, Xingwei,Liu, Bingxian,Yang, Lingyun
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supporting information
p. 7199 - 7204
(2021/09/22)
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- HETEROCYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING SAME
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The present specification relates to a heterocyclic compound represented by Chemical Formula 1, and an organic light emitting device comprising the same.
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Paragraph 0145-0147
(2020/05/14)
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- Ag-Catalyzed Cyclization of Arylboronic Acids with Elemental Selenium for the Synthesis of Selenaheterocycles
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A general method for the synthesis of five-membered and six-membered selenaheterocycles through Ag-catalyzed C?Se bond-forming reaction is reported. This reaction proceeds via intramolecular cyclization of arylboronic acids with selenium powder. Preliminary mechanism studies demonstrate that this transformation involves a selenium-centred radical intermediate. (Figure presented.).
- Gao, Wen-Xia,Huang, Xiao-Bo,Liu, Miao-Chang,Wu, Hua-Yue,Zhang, Xue,Zhou, Yun-Bing
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supporting information
p. 5639 - 5644
(2020/11/30)
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- Palladium (II)–Salan Complexes as Catalysts for Suzuki–Miyaura C–C Cross-Coupling in Water and Air. Effect of the Various Bridging Units within the Diamine Moieties on the Catalytic Performance
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Water-soluble salan ligands were synthesized by hydrogenation and subsequent sulfonation of salens (N,N’-bis(slicylidene)ethylenediamine and analogues) with various bridging units (linkers) connecting the nitrogen atoms. Pd (II) complexes were obtained in reactions of sulfosalans and [PdCl4]2?. Characterization of the ligands and complexes included extensive X-ray diffraction studies, too. The Pd (II) complexes proved highly active catalysts of the Suzuki–Miyaura reaction of aryl halides and arylboronic acid derivatives at 80 ?C in water and air. A comparative study of the Pd (II)–sulfosalan catalysts showed that the catalytic activity largely increased with increasing linker length and with increasing steric congestion around the N donor atoms of the ligands; the highest specific activity was 40,000 (mol substrate) (mol catalyst × h)?1. The substrate scope was explored with the use of the two most active catalysts, containing 1,4-butylene and 1,2-diphenylethylene linkers, respectively.
- Bunda, Szilvia,Joó, Ferenc,Kathó, ágnes,Udvardy, Antal,Voronova, Krisztina
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supporting information
(2020/09/18)
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- Organocatalyst in Direct C(sp2)-H Arylation of Unactivated Arenes: [1-(2-Hydroxyethyl)-piperazine]-Catalyzed Inter-/Intra-molecular C-H Bond Activation
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This article describes the identification of 1-(2-hydroxyethyl)-piperazine as a new, cost-effective, highly efficient organocatalyst, which promotes both inter- A nd intra-molecular direct C(sp2)-H arylations of unactivated arenes in the presence of potassium tert-butoxide. While the inter-molecular C-H arylation of unactivated benzenes with aryl halides (Ar-X; X = I, Br, Cl) toward biaryl syntheses underwent smoothly in the presence of only 10 mol percent organocatalyst, the intra-molecular C-H arylation catalytic system composed of 40 mol percent each of the catalyst and the additive (4-dimethylaminopyridine (DMAP)). The novel catalyst was also able to perform both inter- A nd intra-molecular direct arylations simultaneously in a single pot. The mechanistic studies confirmed the involvement of aryl radical anions and proceeded via a single-electron-transfer (SET) mechanism. The large substrate scope, high functional group tolerance, competition experiments, gram-scale synthesis, and kinetic studies further highlight the importance and versatile nature of the methodology as well as the compatibility of the new catalyst. To the best of our knowledge, this is the first report on any organocatalyst that reported detailed investigations of both inter- A nd intra-molecular direct C(sp2)-H arylations of unactivated arenes in a single representation.
- Yadav, Lalit,Tiwari, Mohit K.,Shyamlal, Bharti Rajesh Kumar,Chaudhary, Sandeep
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p. 8121 - 8141
(2020/07/16)
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- Generation of Organozinc Reagents by Nickel Diazadiene Complex Catalyzed Zinc Insertion into Aryl Sulfonates
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The generation of arylzinc reagents (ArZnX) by direct insertion of zinc into the C?X bond of ArX electrophiles has typically been restricted to iodides and bromides. The insertions of zinc dust into the C?O bonds of various aryl sulfonates (tosylates, mesylates, triflates, sulfamates), or into the C?X bonds of other moderate electrophiles (X=Cl, SMe) are catalyzed by a simple NiCl2–1,4-diazadiene catalyst system, in which 1,4-diazadiene (DAD) stands for diacetyl diimines, phenanthroline, bipyridine and related ligands. Catalytic zincation in DMF or NMP solution at room temperature now provides arylzinc sulfonates, which undergo typical catalytic cross-coupling or electrophilic substitution reactions.
- Klein, Philippe,Lechner, Vivien Denise,Schimmel, Tanja,Hintermann, Lukas
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supporting information
p. 176 - 180
(2019/12/11)
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- A ferrocene-templated Pd-bearing molecular reactor
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High-yield, chromatography-free syntheses of a ferrocene-templated molecular cage and its Pd-bearing derivative are presented. The formation of a symmetric cage-type structure was confirmed by single-crystal X-ray diffraction analysis. The Pd-bearing cage was used as an innovative catalyst for the efficient synthesis of 1,1'-biphenyls under mild conditions. The presented catalyst is reusable and 1,1'-biphenyls can be obtained efficiently in a gram scale process.
- Gunka, Piotr A.,Kasprzak, Artur
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supporting information
p. 6974 - 6979
(2020/06/04)
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- Palladium-catalysed room-temperature Suzuki–Miyaura coupling in water extract of pomegranate ash, a bio-derived sustainable and renewable medium
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An agro waste-derived, ‘water extract of pomegranate ash’ (WEPA), has been utilized for the first time as a renewable medium for Pd(OAc)2-catalysed Suzuki–Miyaura cross-coupling at room temperature. This method offers a simple and sustainable synthesis of biaryls from aryl halides and arylboronic acids under ligand- and external base-free aerobic and ambient conditions. This method has been found effective for both activated and unactivated aryl halides in the production of biaryls with moderate to nearly quantitative yields. The protocol shows high chemoselectivity over identical/similar reactive sites in aryl halides (i.e. selectivity over identical halogens or different halogens of aryl halides). This method exhibits high regioselectivity, i.e. the selective reactivity of a halogen over other identical halogens at different positions on the aromatic nucleus. Therefore, we disclose here a clean, benign, substantial chemo- and regioselective and highly economic alternative method for the palladium-assisted synthesis of biaryls using an agro waste-derived medium.
- Appa, Rama Moorhy,Prasad, S. Siva,Lakshmidevi, Jangam,Naidu, Bandameeda Ramesh,Narasimhulu, Manchala,Venkateswarlu, Katta
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- N,S-chelating triazole-thioether ligand for highly efficient palladium-catalyzed Suzuki reaction
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1,2,3-Triazole-thioether compounds could serve as efficient ligands for Pd-catalyzed Suzuki reactions of various aryl iodides, bromides and chlorides. The reactions feature wide substrate scope and mild reaction conditions. Besides, shorter reaction time, lower catalyst loadings and quantitative yields with a turnover-frequency (TOF) value of up to 11,880 h?1 are other advantageous of this attractive protocol. The crystal structure analyses and computational studies revealed that the higher catalytic activity of the corresponding chelated palladium complex ascribed to the lower energy gap and the lower redox potential.
- Yan, Qiong,Zheng, Lei,Li, Miaomiao,Chen, Yunfeng
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p. 101 - 105
(2019/07/19)
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- Visible-Light-Promoted, Catalyst-Free Gomberg-Bachmann Reaction: Synthesis of Biaryls
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Biaryls were synthesized via a novel visible-light-promoted Gomberg-Bachmann reaction that does not require a photosensitizer or any metal reagents. The formation of an electron donor-acceptor complex between aryl diazonium salts and pyridine allows, under visible-light irradiation, the synthesis of biaryls in moderate-to-high yields.
- Lee, Juyoung,Hong, Boseok,Lee, Anna
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p. 9297 - 9306
(2019/08/12)
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- Transition-Metal-Free Heterobiaryl Synthesis via Aryne Coupling
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We disclose, for the first time, an efficient route for the construction of various heterobiaryl backbones in fair to excellent yields using the Aryne coupling methodology. This study outlined the remarkable effect of external chelating ligands and salt additives on the heterocyclic partner reactivity in the aryne coupling reaction.
- Saied, Tarak,Demangeat, Catherine,Panossian, Armen,Leroux, Frédéric R.,Fort, Yves,Comoy, Corinne
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supporting information
p. 5275 - 5284
(2019/03/27)
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- Transition-Metal-Free Approach for the Direct Arylation of Thiophene: Experimental and Theoretical Investigations towards the (Het)-Aryne Route
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This paper presents the results of our investigations on the arylation of thiophene using the transition-metal-free “aryne coupling” methodology. The reaction was studied by both experiment and computation (density functional theory) and comparison with phenyllithium was established. In parallel, the effects of the ligand and the salt on the coupling reaction were examined. The results underline the remarkable effect of such additives on the coupling reaction and the potency of the method to construct hetaryl–aryl backbones which open up promising access to a wide range of heterobiaryl structures using the novel “Het-Aryne” route.
- Demangeat, Catherine,Saied, Tarak,Ramozzi, Romain,Ingrosso, Francesca,Ruiz-Lopez, Manuel,Panossian, Armen,Leroux, Frédéric R.,Fort, Yves,Comoy, Corinne
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p. 547 - 556
(2018/12/11)
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- Oxidant-free oxidation of C-H bonds by cathodic hydrogen evolution: A phosphonic Kolbe oxidation/cyclization process
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An anodic oxidation/cyclization of 2-(aryl)aryl phosphonic acid monoesters for ethoxy dibenzooxaphosphorin oxide synthesis has been developed. This unprecedented electrochemical oxidation reaction proceeds at room temperature with no oxidant or electrolyt
- Zhang, Lei,Zhang, Zhenxing,Zhang, Jianning,Li, Kangle,Mo, Fanyang
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supporting information
p. 3916 - 3920
(2018/09/11)
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- Visible-Light Induced Radical Silylation for the Synthesis of Dibenzosiloles via Dehydrogenative Cyclization
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A visible-light induced radical silylation to dibenzosiloles from biarylhydrosilanes is described. The products were obtained in satisfactory yields under mild and water/air compatible conditions, providing an efficient and practical method for the synthesis of difunctionalized siloles by using a cheap organic dye photocatalyst. The method is tolerated by a wide range of functional groups and has a broad substrate scope. Light/dark experiments and quantum yield measurements provided support for a photocatalytic pathway rather than a chain process. (Figure presented.).
- Yang, Chao,Wang, Jing,Li, Jianhua,Ma, Wenchao,An, Kun,He, Wei,Jiang, Chao
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supporting information
p. 3049 - 3054
(2018/08/06)
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- Palladium/Norbornene Chemistry: Synthesis of Norbornene-Containing Arylsilanes Involving Double C-Si Bond Formation
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A novel palladium-catalyzed three-component cascade reaction of aryl halides with norbornene and hexamethyldisilane has been described, which allows the simultaneous construction of two C-Si bonds and one C-C bond. The method achieves ortho C-H functionalization of aryl halides through the formation of the five-membered palladacycle, leading to norbornene-containing arylsilanes.
- Xu, Yankun,Liu, Xiaodong,Chen, Wenqi,Deng, Guobo,Liang, Yun,Yang, Yuan
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p. 13930 - 13939
(2018/11/30)
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- Alumina as Solid-State Ligand in Enhancing the Redox Catalytic Property of Iron Oxide Grafted AlSBA-15 towards Arylation of Arene
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2–8 wt % iron has been grafted over SBA-15 and 10 wt % alumina grafted SBA-15 (AlSBA-15) through selective extraction deposition technique using LaFeO3 as iron precursor in acidic solution. DRS-UV spectra confirmed the presence of iron as isolated Fe(III), Fe(III)-clusters and amorphous FeOx oligomers. SEM-EDX mapping, FT-IR, XPS, HR-TEM and 27Al MAS NMR characterisation results confirmed that iron grafted over AlSBA-15 preferentially reside on the alumina. The donor-acceptor interaction of grafted iron ions with alumina atoms displaying Lewis acid properties stabilized iron at higher oxidation state Fe(III+δ). This increased the BE of Fe2p electrons (XPS) and shifted the temperature of iron reduction in 2–8 wt %Fe/AlSBA-15 materials to higher value (600 °C) compared with Fe/SBA-15 (H2-TPR). In arylation of benzene, 8 wt %Fe/AlSBA-15 demonstrated excellent redox catalytic activity with TOF close to homogeneous catalyst and 82 % biphenyl yield. The catalyst demonstrated consistent catalytic performance for 7 cycles.
- Rajendran, Chandran,Thirumoorthy, Kulandaivellu,Satishkumar, Govindaswamy,Landau, Miron V.
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p. 4768 - 4776
(2018/10/02)
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- Rapid Access to Bi- and Tri-Functionalized Dibenzofurans and their Application in Selective Suzuki–Miyaura Cross Coupling Reactions
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Syntheses of 1,2-, 1,3-, 1,4-, 1,8-, 2,4-, 3,4-, 4,8-, 1,2,4-, 1,2,8- and 1,3,4-functionalized dibenzofurans in few steps with good to excellent yields starting from dibenzofuran-1-ol or -4-ol are presented. These rapidly accessible bi- or tri-functionalized building blocks are of great interest for the synthesis of bioactive substances or functional material development. Furthermore, for intermediates containing both a bromine and a triflate moiety, a selective mono-substitution by means of Suzuki–Miyaura reaction (SMR) is described.
- Wern, Caroline,Ehrenreich, Christian,Joosten, Dominik,Stein, Thorsten vom,Buchholz, Herwig,K?nig, Burkhard
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p. 5644 - 5656
(2018/10/09)
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- Synthesis of Bi(hetero)aryls via Sequential Oxidation and Decarboxylation of Benzylamines in a Batch/Fully Automated Continuous Flow Process
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Catalytic dehydrogenative cross-coupling of two C–H bonds represents a green strategy in view of the atom- and step-economy. However, the challenge is to discover a new innovative bond strategy, especially for the direct coupling between Csp2–H
- Mahajan, Bhushan,Aand, Dnyaneshwar,Singh, Ajay K.
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supporting information
p. 2831 - 2835
(2018/06/21)
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- Direct Aryl-Aryl Coupling without Pre-Functionalization Enabled by Excessive Oxidation of Two-Electron Ag(I)/Ag(III) Catalyst
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Reported herein is a catalytic platform for formation of unsymmetrical biaryls by the coupling between inert Csp2?CH3 and Csp2?H via a tandem catalytic strategy. The platform utilizes traditional AgNO3 catalyst and excess amount of K2S2O8 oxidant. The excessive oxidant present converts the traditional one-electron Ag(I)/Ag(II) chemistry to two-electron Ag(I)/Ag(III) one, enabling one-pot synthesis of aryl-aryl scaffolds by using unactivated cheap commodity chemicals. (Figure presented.).
- Singh, Ajay K.,Kim, Min-Gyu,Lee, Hyune-Jea,Singh, Rakhi,Cho, Seung Hwan,Kim, Dong-Pyo
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supporting information
p. 2032 - 2042
(2018/04/11)
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- Gold(i)-catalyzed cross-coupling reactions of aryldiazonium salts with organostannanes
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Gold(i)-catalyzed cross-coupling reactions of aryldiazonium salts with organostannanes are described. This redox neutral strategy offers an efficient approach to diverse biaryls, vinyl arenes and arylacetylenes. Monitoring the reaction with NMR and ESI-MS provided strong evidence for the in situ formation of Ph3PAuIR (R = aryl, vinyl and alkynyl) species which is crucial for the activation of aryldiazonium salts.
- Akram, Manjur O.,Shinde, Popat S.,Chintawar, Chetan C.,Patil, Nitin T.
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supporting information
p. 2865 - 2869
(2018/05/03)
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- Electron Transfer around a Molecular Corner
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The distance dependence of electron transfer (ET) is commonly investigated in linear rigid rod-like compounds, but studies of molecular wires with integrated corners imposing 90° angles are very rare. By using spirobifluorene as a key bridging element and by substituting it at different positions, two isomeric series of donor-bridge-acceptor compounds with either nearly linear or angled geometries were obtained. Photoinduced ET in both series is dominated by rapid through-bond hole hopping across oligofluorene bridges over distances of up to 70 ?. Despite considerable conformational flexibility, direct through-space and through-solvent ET is negligible even in the angled series. The independence of the ET rate constant on the total number of fluorene units in the angled series is attributed to a rate-limiting tunneling step through the spirobifluorene corner. This finding is relevant for multidimensional ET systems and grids in which individual molecular wires are interlinked at 90° angles.
- Schmidt, Hauke C.,Larsen, Christopher B.,Wenger, Oliver S.
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supporting information
p. 6696 - 6700
(2018/03/26)
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- ONE STEP DIRECT ARYLATION OF COMMODITY CHEMICALS TO SPECIALTY CHEMICALS BY TANDEM CATALYTIC PLATFORM
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The present invention relates to a continuous direct arylation process based on a tandem catalyst for synthesizing specialty chemicals. A method for synthesizing an aryl-aryl structure from a substrate selected from the group consisting of benzyl alcohol, benzyl amine and toluene which are low value added compounds is developed using a silver ion-containing tandem catalyst. The method is applied for synthesizing hexaphenyl arylene and can be applied for synthesizing high value added compounds (not only natural substances and chemical compounds but pharmaceutical and agricultural pesticide relative fields) directly from primary raw materials through the reaction.COPYRIGHT KIPO 2017
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Paragraph 0063; 0067; 0106
(2018/02/28)
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- The Rolling-Up of Oligophenylenes to Nanographenes by a HF-Zipping Approach
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Intramolecular aryl–aryl coupling is the key transformation in the rational synthesis of nanographenes and nanoribbons. In this respect the C?F bond activation was shown to be a versatile alternative enabling the synthesis of several unique carbon-based nanostructures. Herein we describe an unprecedentedly challenging transformation showing that the C?F bond activation by aluminum oxide allows highly effective domino-like C?C bond formation. Despite the flexible nature of oligophenylene-based precursors efficient regioselective zipping to the target nanostructures was achieved. We show that fluorine positions in the precursor structure unambiguously dictate the “running of the zipping-program” which results in rolling-up of linear oligophenylene chains around phenyl moieties yielding target nanographenes. The high efficiency of zipping makes this approach attractive for the synthesis of unsubstituted nanographenes which are difficult to obtain in pure form by other methods.
- Steiner, Ann-Kristin,Amsharov, Konstantin Y.
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supporting information
p. 14732 - 14736
(2017/10/23)
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- P(O)R2-Directed Enantioselective C-H Olefination toward Chiral Atropoisomeric Phosphine-Olefin Compounds
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An effective synthesis of chiral atropoisomeric biaryl phosphine-olefin compounds via palladium-catalyzed enantioselective C-H olefination has been developed for the first time. The reactions are operationally simple, tolerate wide functional groups, and have a good ee value. Notably, P(O)R2 not only acts as the directing group to direct C-H activation in order to make a useful ligand but also serves to facilitate composition of the product in a useful manner in this transformation.
- Li, Shi-Xia,Ma, Yan-Na,Yang, Shang-Dong
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supporting information
p. 1842 - 1845
(2017/04/11)
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- Synthetic method for 9,10-benzophenanthrene compound
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The invention discloses a synthetic method for a 9,10-benzophenanthrene compound. The synthetic method comprises the following concrete steps: dissolving a compound as shown in a formula (2) which is described in the specification and another compound as shown in a formula (4) which is described in the specification in N,N-dimethyl formamide under the protection of inert gas; and carrying out a reaction at 120 to 140 DEG C under the action of copper trifluoromethanesulfonate, sodium carbonate and caesium acetate so as to obtain the 9,10-benzophenanthrene compound as shown in a formula (I) which is described in the specification. According to the invention, 2-bromobiphenyl is used as a raw material, diaryl iodate is used as an arylation reagent, bivalent copper is used as a catalyst, and sodium carbonate and caesium acetate are used as mixed base; the synthetic method has the characteristics of usage of easily available raw materials, short reaction time, high yield, etc.; and as a simplest graphene monomer, the synthesized 9,10-benzophenanthrene compound good application prospects in the field of organic photoelectricity.
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Paragraph 0031; 0033
(2018/01/09)
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- A Sustainable Heterogeneous Iron Catalyst Fe/SBA-15 towards Direct Arylation of Unactivated C(sp3)?H and C(sp2)?H Bonds with Arenes
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Iron grafted over mesoporous silica (8 wt %Fe/SBA-15) is a sustainable, efficient heterogeneous iron catalyst for direct arylation of biphenyl methane C(sp3)?H and benzene C(sp2)?H bonds. The selective extraction deposition (SED) technique was adopted to graft iron easily over the mesoporous support SBA-15 by using LaFeO3 as an iron precursor. The synthesized catalyst has been characterized by EPR spectroscopy, diffuse reflectance UV/Vis spectroscopy, and temperature programmed reduction (TPR) analysis to understand the coordination environment and state of oxidic iron species grafted over the mesoporous SBA-15. TPR results confirm the presence of isolated, clustered, oligomeric oxidic iron species in the catalyst. The adopted SED technique is highly successful for grafting 8 wt % iron into the mesopores of SBA-15 without forming iron oxide particles. Unlike homogeneous iron, the 8 wt %Fe/SBA-15 catalyst does not need support from an electron-withdrawing group and additives to carry out arylation of benzene and could be successfully recycled five times.
- Rajendran,Satishkumar
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p. 1284 - 1291
(2017/04/14)
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- Method for preparing coupling arene from aryl halide by ionizing, discharging and coupling
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The invention discloses a method for preparing coupling arene from aryl halide by ionizing, discharging and coupling. The method comprises the following steps: placing a magnetic stirrer into a three-necked flask and adding aryl halide occupying 1/2 flask, thereby finishing the assembling of an ionizing reaction device; placing the ionizing reaction device into an oil bath pan, introducing inert gas into a reaction system, removing air from the reaction system, starting stirring and heating in the oil bath pan to make aryl halide flow back, and meanwhile, introducing water into a ball-shaped condensation pipe for cooling; starting a high-voltage power generator, and introducing powerful arc generated into the three-necked flask through a metal electrode, thereby ionizing and decomposing aryl halide steam and generating a coupling arene compound; stopping ionizing and heating when solids are separated or the backflow of aryl halide is slowed in a round-bottom flask, and then ending the reaction; recrystallizing or performing reduced pressure distillation purification on the coupling arene product in the flask, thereby acquiring the coupling arene product. The method disclosed by the invention has the advantages of low cost, high efficiency, environmental protection, and the like.
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Paragraph 0029-0043; 0044-0048
(2017/09/26)
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- Oriented Au nanoplatelets on graphene promote Suzuki-Miyaura coupling with higher efficiency and different reactivity pattern than supported palladium
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Facet 1?1?1 oriented Au nanoplatelets (20–40?nm wide, 3–4?nm height) grafted on graphene (Au ̄/fl-G) are about three orders of magnitude more efficient than Pd nanoparticles supported on graphene to promote Suzuki-Miyaura coupling. In contrast to Pd cataly
- Candu, Natalia,Dhakshinamoorthy, Amarajothi,Apostol, Nicoleta,Teodorescu, Cristian,Corma, Avelino,Garcia, Hermenegildo,Parvulescu, Vasile I.
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- Mild, visible light-mediated decarboxylation of aryl carboxylic acids to access aryl radicals
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Herein we present the first example of aryl radical formation via the visible light-mediated decarboxylation of aryl carboxylic acids using photoredox catalysis. This method constitutes a mild protocol for the decarboxylation of cheap and abundant aryl carboxylic acids and tolerates both electron-rich substrates and those lacking ortho-substitution. The in situ formation of an acyl hypobromite is proposed to prevent unproductive hydrogen atom abstraction and trapping of the intermediate aroyloxy radical, enabling mild decarboxylation.
- Candish,Freitag,Gensch,Glorius
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p. 3618 - 3622
(2017/07/11)
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- Arenediazonium Tosylates (ADTs) as Efficient Reagents for Suzuki-Miyaura Cross-Coupling in Neat Water
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A simple, convenient, and environment-friendly procedure for the preparation of substituted biaryls via Suzuki-Miyaura cross-coupling- was developed. The use of arenediazonium tosylates and corresponding boron compounds allows a conversion in neat water in the presence of commercially available Pd(OAc)2 under mild conditions with tolerance to a wide range of functional groups. A procedure particularly useful for the synthesis of di-ortho-substituted biaryls was developed.
- Kutonova, Ksenia V.,Jung, Nicole,Trusova, Marina E.,Filimonov, Victor D.,Postnikov, Pavel S.,Br?se, Stefan
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p. 1680 - 1688
(2017/03/21)
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- Rhodium-catalyzed intramolecular C-H silylation by silacyclobutanes
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Silacyclobutane was discovered to be an efficient C-H bond silylation reagent. Under the catalysis of RhI/TMS-segphos, silacyclobutane undergoes sequential C-Si/C-H bond activations, affording a series of π-conjugated siloles in high yields and regioselectivities. The catalytic cycle was proposed to involve a rarely documented endocyclic β-hydride elimination of five-membered metallacycles, which after reductive elimination gave rise to a Si-RhI species that is capable of C-H activation. Old reagent, new reactivity: Silacyclobutane was discovered to be an efficient C-H bond silylation reagent under the catalysis of Rh/TMS-segophos. This new reactivity was attributed to a key Si-RhI intermediate formed through a Si-C activation, endocyclic β-H elimination and reductive elimination cascade. A wide array of siloles was obtained in high yields and excellent regioselectivities.
- Zhang, Qing-Wei,An, Kun,Liu, Li-Chuan,Guo, Shuangxi,Jiang, Chenran,Guo, Huifang,He, Wei
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supporting information
p. 6319 - 6323
(2016/05/24)
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- Pd-catalyzed one-pot sequential unsymmetrical cross-coupling reactions of aryl/heteroaryl 1,2-dihalides
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Efficient, step-economic, Pd(ii)-catalyzed one-pot sequential Sonogashira/Sonogashira, Sonogashira/Suzuki, Sonogashira/Heck, Suzuki/Sonogashira, Suzuki/Suzuki, Suzuki/Heck, Heck/Sonogashira, Heck/Suzuki and Heck/Heck cross coupling reactions of sterically hindered aryl/heteroaryl 1,2-dihalides have been developed. The present methodology allows the conversion of easily available aryl/heteroaryl 1,2-dihalides into synthetically useful unsymmetrically substituted arenes/heteroarenes in good to excellent yields under mild reaction conditions. This methodology is a powerful tool for building a versatile substrate which can be utilized for the synthesis of various organic scaffolds.
- Danodia, Abhinandan K.,Saunthwal, Rakesh K.,Patel, Monika,Tiwari, Rakesh K.,Verma, Akhilesh K.
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supporting information
p. 6487 - 6496
(2016/07/15)
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- 9-Silafluorenes via base-promoted homolytic aromatic substitution (BHAS) - The electron as a catalyst
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Transition-metal-free intramolecular radical silylation of 2-diphenylsilylbiaryls via base-promoted homolytic aromatic substitution (BHAS) to give 9-silafluorenes is reported. 2-Diphenylsilylbiaryls are readily prepared, and cross dehydrogenative silylation occurs with tert-butylhydroperoxide (TBHP) as a cheap stoichiometric oxidant in the presence of a small amount of tetrabutylammonium iodide (TBAI) as an initiator. These cyclizations are catalyzed by the electron.
- Leifert, Dirk,Studer, Armido
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supporting information
p. 386 - 389
(2015/01/30)
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- Catalytic chemical amide synthesis at room temperature: One more step toward peptide synthesis
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An efficient method has been developed for direct amide bond synthesis between carboxylic acids and amines via (2-(thiophen-2-ylmethyl)phenyl)boronic acid as a highly active bench-stable catalyst. This catalyst was found to be very effective at room temperature for a large range of substrates with slightly higher temperatures required for challenging ones. This methodology can be applied to aliphatic, α-hydroxyl, aromatic, and heteroaromatic acids as well as primary, secondary, heterocyclic, and even functionalized amines. Notably, N-Boc-protected amino acids were successfully coupled in good yields with very little racemization. An example of catalytic dipeptide synthesis is reported.
- Mohy El Dine, Tharwat,Erb, William,Berhault, Yohann,Rouden, Jacques,Blanchet, Jér?me
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p. 4532 - 4544
(2015/05/13)
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- Synthesis of Biaryls via Benzylic C-C Bond Cleavage of Styrenes and Benzyl Alcohols
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A metal-free oxidative coupling of styrenes and benzyl alcohols with arenes has been developed for the synthesis of biaryls. The reaction features a conspicuous benzylic C-C bond cleavage of styrenes and benzyl alcohols. The reaction with both substrates proceeds through a common aldehydic intermediate formed through oxidative C-C bond cleavage of alkene and oxidation of benzyl alcohols. The reaction proceeds efficiently over a broad range of substrates with excellent functional group tolerance.
- Kumar, Arvind,Shah, Bhahwal Ali
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supporting information
p. 5232 - 5235
(2015/11/18)
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- Synthesis of Fluoren-9-ones and Ladder-Type Oligo-p-phenylene Cores via Pd-Catalyzed Carbonylative Multiple C-C Bond Formation
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A new route to various substituted fluoren-9-ones has been developed via an efficient Pd-catalyzed carbonylative multiple C-C bond formation. Under a CO atmosphere, using commercially available aryl halides and arylboronic acids as substrates, this three-component reaction proceeded smoothly in moderate to excellent yields with good functional-group compatibility. The mechanistic investigations suggested a sequential process for the reaction that forms o-bromobiaryls in the first stage followed by a cyclocarbonylation reaction. This chemistry has been successfully extended to construct ladder-type oligo-p-phenylene cores. (Chemical Equation Presented).
- Song, Juan,Wei, Fuliang,Sun, Wei,Li, Ke,Tian, Yanan,Liu, Chao,Li, Yali,Xie, Linghai
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supporting information
p. 2106 - 2109
(2015/05/13)
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- Palladium-catalyzed P(O)R2 directed C-H arylation to synthesize electron-rich polyaromatic monophosphorus ligands
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Palladium-catalyzed arylation of (diisopropylphosphoryl)biphenyl skeleton derivatives by the P(O)R2 directed C-H functionalization was reported. The related products were obtained in high regioselectivity and good functional group tolerance was observed. This reaction provided a new and efficient pathway for the synthesis of polyaromatic monophosphorus ligands. The Royal Society of Chemistry.
- Hu, Rong-Bin,Zhang, Heng,Zhang, Xiao-Yu,Yang, Shang-Dong
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supporting information
p. 2193 - 2195
(2014/02/14)
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- Palladium-catalyzed R2(O)P directed C(sp2)-H acetoxylation
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A novel and efficient Pd-catalyzed C-H acetoxylation is described. The approach uses R2(O)P as a directing group to synthesize various substituted 2′-phosphorylbiphenyl-2-OAc compounds. Notably, the reaction exhibits smooth operation under mild conditions and shows good functional group tolerance. Products are obtained with high selectivity and yields. This journal is the Partner Organisations 2014.
- Zhang, Heng,Hu, Rong-Bin,Zhang, Xiao-Yu,Li, Shi-Xia,Yang, Shang-Dong
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supporting information
p. 4686 - 4689
(2014/05/06)
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- Synthesis of ethoxy dibenzooxaphosphorin oxides through palladium-catalyzed C(sp2)-H activation/C-O formation
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We report an efficient Pd-catalyzed C(sp2)-H activation/C-O bond formation for the synthesis of ethoxy dibenzooxaphosphorin oxides from 2-(aryl)arylphosphonic acid monoethyl esters under aerobic conditions.
- Shin, Seohyun,Kang, Dongjin,Jeon, Woo Hyung,Lee, Phil Ho
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supporting information
p. 1220 - 1227
(2014/06/10)
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- Triphyrin catalyzed direct C-H arylation of benzene with aryl halides
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Transition-metal free direct C-H arylation of benzene with aryl halides was achieved by meso-aryl-substituted [14]triphyrins(2.1.1) catalysts in an air atmosphere. Various aryl halides underwent successful direct C-H arylation of benzene to give moderate to high yields of biaryls. A radical mechanism is proposed for this triphyrin catalyzed C-H arylation reaction.
- Xue, Zhao-Li,Qian, Ying Ying,Chan, Kin Shing
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supporting information
p. 6180 - 6183
(2015/02/19)
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- Debromination of bromobenzene induced by hydrated electrons in aqueous solution
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The nanosecond laser flash photolysis (LFP) experiments were adopted to investigate the kinetics and mechanisms of the reaction between bromobenzene and hydrated electrons (eaq) in aqueous solution. The results showed that the rate constants of
- Yuan, Haixia,Pan, Huxiang,Shi, Jin,Li, Hongjing,Dong, Wenbo
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p. 4211 - 4214
(2014/08/05)
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- Pd(II)-catalyzed Ph2(O)P-directed C-H olefination toward phosphine-alkene ligands
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The Pd(II)-catalyzed Ph2(O)P-directed C-H olefination to synthesize alkene-phosphine compounds is reported. In contrast to previous examples of various directing groups that guide selective C-H activation, the Ph2(O)P group not only acts as the directing group but also serves to construct the alkene-phosphine ligands. The monoprotected amino acid (MPAA) ligand Ac-Leu-OH is found to promote this reaction in a significant manner.
- Wang, Hong-Li,Hu, Rong-Bin,Zhang, Heng,Zhou, An-Xi,Yang, Shang-Dong
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supporting information
p. 5302 - 5305
(2013/11/06)
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- Pd(II)-catalyzed C(sp2)-H hydroxylation with R 2(O)P-coordinating group
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A novel R2(O)P-directed Pd(II)-catalyzed C-H hydroxylation to synthesize various substituted 2′-phosphorylbiphenyl-2-ol compounds is described. Notably, the reaction operates under mild conditions and shows good functional group tolerance, high selectivity, and yield.
- Zhang, Hong-Yu,Yi, Hong-Ming,Wang, Gang-Wei,Yang, Bin,Yang, Shang-Dong
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supporting information
p. 6186 - 6189
(2014/01/17)
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