- Beta zeolite supported on silicon carbide for Friedel-Crafts fixed-bed reactions
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Beta zeolite supported on silicon carbide, with high thermal conductivity and high mechanical strength, was successfully used as an active and stable catalyst for Friedel-Crafts reactions in a fixed bed configuration.
- Wine, Gauthier,Matta, Joseph,Tessonnier, Jean-Philippe,Pham-Huu, Cuong,Ledoux, Marc-Jacques
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- DDQ/PbO2: A novel oxidation system for hindered electron rich benzhydrols
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A convenient mild protocol for oxidation of highly hindered electron rich benzhydrols using DDQ / PbO2 (has been developed.
- Kalena,Jadhav,Banerji
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Read Online
- Synthesis of 2-(1-Alkoxyvinyl)anilines by Palladium/Norbornene-Catalyzed Amination Followed by Termination with Vinyl Ethers
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A palladium/norbornene-catalyzed ortho-amination and ipso vinyl ether termination reaction of iodoarenes is reported. The benzyl vinyl ether serves as an efficient alternative carbonyl source in palladium/norbornene catalysis for the final ipso termination reaction to give [1-(benzyloxy)vinyl]arenes, which readily undergo hydrolysis to deliver methyl ketones under aqueous acidic conditions. The final Heck termination reaction with vinyl ethers has high branched/linear selectivity. This reaction tolerates a range of iodoarene and O-benzoylhydroxylamine substrates, and it provides a convenient way to prepare o-acetylanilines. The synthetic utility of [1-(benzyloxy)vinyl]arenes and the corresponding ketones is briefly investigated. (Figure presented.).
- Wang, Jie,Gu, Zhenhua
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- Beta zeolite supported on a macroscopic pre-shaped SiC as a high performance catalyst for liquid-phase benzoylation
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Preparation and characterisation of a highly active and stable beta zeolite supported on a pre-shaped silicon carbide catalyst for the benzoylation reaction in liquid phase.
- Wine,Tessonnier,Pham-Huu,Ledoux
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- Zirconium-doped porous magadiite heterostructures upon 2D intragallery in situ hydrolysis-condensation-polymerization strategy for liquid-phase benzoylation
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Novel zirconium-doped porous magadiite heterostructures (PMH-xZr, x = Zr/Si molar ratio) are fabricated by two-dimensional intragallery cosurfactant-directing in situ hydrolysis-condensation-polymerization method of TEOS and Zr-n-propoxide from synthetic Na-magadiite and characterized systematically by XRD, SEM/(HR)TEM, 29Si MAS NMR, BET, UV-vis DRS, NH3-TPD, pyridine FT-IR, and XPS techniques. The results indicate that the obtained PMH-xZr materials possess high surface area and high thermal stability upon effective assembly of interlayer Zr-doped meso-structural silica and the layers of magadiite. The PMH-xZr samples with x 0.2 show successful incorporation of Zr into the lattice of interlayer mesostructural silica framework leading to considerably generated Bronsted sites Zr-O(H)-Si and obviously increased Lewis sites Zr-O-Si along with well-kept layered supermicro-mesostructure, while PMH-0.2Zr shows delaminated layers. PMH-0.1Zr exhibits the highest liquid-phase benzoylation activity of anisole with benzoyl chloride (Conv. 99.5%) and yield for 4-methoxybenzophenone (4-MBP) (94.1%) due to the strongest synergy between the high concentration of surface Bronsted sites and supermicro-mesostructure. PMH-0.1Zr can be reused by no further chemical treatment for at least five runs with a slightly reduced 4-MBP yield. These PMH-xZr materials can serve as a promising solid acid catalyst and/or acidic support with high surface area and thermal stability in broad range of catalysis applications.
- Ma, Yuewen,Sun, Huan,Sun, Qi,Zhang, Hui
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- 12-Tungstophosphoric acid niched in Zr-based metal-organic framework: a stable and efficient catalyst for Friedel-Crafts acylation
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Heteropolyacids (HPA) are well known for their versatile solid acid catalysis in diverse chemical reactions, however they suffer from low surface area (2/g) and leaching into the reactions media, which reduce their prospects as industrial catalyst. Herein, a novel hybrid material HPW@Zr-BTC, composed of 12-tungstophoric acid (HPW) and ZrIV-benzene tri-carboxylate (Zr-BTC) metal-organic framework (MOF), was prepared via one-pot solvothermal method. Excellent HPW loading up to 32.3 wt% was achieved, and HPW@Zr-BTC composite proved to be highly stable, besides the crystalline morphology of Zr-BTC was intact. The catalytic activity of the hybrid composite was explored via Friedel-Crafts acylation of anisole with benzoyl chloride. The 28.2 wt% HPW@Zr-BTC showed excellent catalytic performance, with 99.4% anisole conversion and 97.6% yield (pmethoxybenzophenone) under solvent free conditions. Excellent retention of catalytic activity was achieved after at least five consecutive runs due to non-observable HPW leaching. The promising activity and stability of the catalyst forecasted its potential industrial applications.
- Ullah, Latif,Zhao, Guoying,Xu, Zichen,He, Hongyan,Usman, Muhammad,Zhang, Suojiang
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- Asymmetric Transfer Hydrogenation of Diaryl Ketones with Ethanol Catalyzed by Chiral NCP Pincer Iridium Complexes
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The use of a chiral (NCP)Ir complex as the precatalyst allowed for the discovery of asymmetric transfer hydrogenation of diaryl ketones with ethanol as the hydrogen source and solvent. This reaction was applicable to various ortho-substituted diaryl keontes, affording benzhydrols in good yields and enantioselectivities. This protocol could be carried out in a gram scale under mild reaction conditions. The utility of the catalytic system was highlighted by the synthesis of the key precursor of (S)-neobenodine.
- Huang, Zheng,Liu, Guixia,Qian, Lu,Tang, Xixia,Wang, Yulei
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supporting information
(2022/02/23)
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- Mechanochemical Solvent-Free Suzuki–Miyaura Cross-Coupling of Amides via Highly Chemoselective N?C Cleavage
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Although cross-coupling reactions of amides by selective N?C cleavage are one of the most powerful and burgeoning areas in organic synthesis due to the ubiquity of amide bonds, the development of mechanochemical, solid-state methods remains a major challe
- Ma, Yangmin,Shao, Lei,Szostak, Michal,Wang, Ruihong,Zhang, Jin,Zhang, Pei
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supporting information
(2022/01/04)
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- Evaluation of Cyclic Amides as Activating Groups in N-C Bond Cross-Coupling: Discovery of N-Acyl-δ-valerolactams as Effective Twisted Amide Precursors for Cross-Coupling Reactions
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The development of efficient methods for facilitating N-C(O) bond activation in amides is an important objective in organic synthesis that permits the manipulation of the traditionally unreactive amide bonds. Herein, we report a comparative evaluation of a series of cyclic amides as activating groups in amide N-C(O) bond cross-coupling. Evaluation of N-acyl-imides, N-acyl-lactams, and N-acyl-oxazolidinones bearing five- and six-membered rings using Pd(II)-NHC and Pd-phosphine systems reveals the relative reactivity order of N-activating groups in Suzuki-Miyaura cross-coupling. The reactivity of activated phenolic esters and thioesters is evaluated for comparison in O-C(O) and S-C(O) cross-coupling under the same reaction conditions. Most notably, the study reveals N-acyl-δ-valerolactams as a highly effective class of mono-N-acyl-activated amide precursors in cross-coupling. The X-ray structure of the model N-acyl-δ-valerolactam is characterized by an additive Winkler-Dunitz distortion parameter ?(τ+χN) of 54.0°, placing this amide in a medium distortion range of twisted amides. Computational studies provide insight into the structural and energetic parameters of the amide bond, including amidic resonance, N/O-protonation aptitude, and the rotational barrier around the N-C(O) axis. This class of N-acyl-lactams will be a valuable addition to the growing portfolio of amide electrophiles for cross-coupling reactions by acyl-metal intermediates.
- Bisz, Elwira,Chen, Hao,Dziuk, B?a?ej,Ejsmont, Krzysztof,Lalancette, Roger,Pyle, Daniel J.,Rahman, Md. Mahbubur,Szostak, Michal,Szostak, Roman,Wang, Qi
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p. 10455 - 10466
(2021/07/31)
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- Tetra- And Dinuclear Palladium Complexes Based on a Ligand of 2,8-Di-2-pyridinylanthyridine: Preparation, Characterization, and Catalytic Activity
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Complexation of L [L = 5-phenyl-2,8-di-2-pyridinyl-anthyridine] with [Pd(CH3CN)4](BF4)2 and [Pd(CH3CN)3Cl](BF4) in a molar ratio of 1:2 rendered the corresponding dinuclear complexes [Pd2L (CH3CN)4](BF4)4 (1) and [Pd2L (CH3CN)2Cl2](BF4)2 (2), respectively. However, treatment of L with (COD)PdCl2 followed by anion exchange yielded a tetranuclear complex [Pd4L3Cl4](PF6)4(4a). Structures of these complexes are characterized by both spectroscopy and X-ray crystallography. Interconversion of these three complexes was studied via the manipulation of stoichiometric ratio of ligand to metal precursor. The catalytic activity of these complexes for carbonylative Suzuki-Miyaura cross-coupling was investigated. Complex 2 shows an excellent catalytic activity on the reaction of aryl iodide with arylboronic acid in the presence of atmospheric pressure of CO to give the corresponding benzophenones.
- Lin, Shih-Chieh Aaron,Liu, Shiuh-Tzung,Liu, Yi-Hung,Peng, Shie-Ming,Su, Bo-Kai
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p. 2081 - 2089
(2021/07/26)
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- 2-(2,2-DIARYLETHYL)-CYCLIC AMINE DERIVATIVE OR SALT, SYNTHESIS THEREOF, AND APPLICATION AND COMPOSITION THEREOF
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The disclosure relates to a 2-(2,2-diarylethyl)-cyclic amine derivative or salt, a synthesis method, an application and a composition thereof. Biological activity test shows that this kind of 2-(2,2-diarylethyl)-cyclic amine derivative has good M-receptor antagonistic activity; and can be used as an active component of drugs for the treatment of the diseases mediated or regulated by muscarinic receptors, such as asthma, chronic obstructive pulmonary disease (COPD), overactive bladder (OAB), bronchospasm with chronic obstructive pulmonary disease, visceral spasm, irritable bowel syndrome, Parkinson's disease, depression or anxiety, schizophrenia and related mental diseases.
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Paragraph 0383-0384
(2021/05/28)
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- Palladium supported on MRGO@CoAl-LDH catalyzed reductive carbonylation of nitroarenes and carbonylative Suzuki coupling reactions using formic acid as liquid CO and H2 source
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In the present study, a heterogeneous palladium catalyst system, Pd nanoparticles supported on MRGO@CoAl-LDH, was synthesized and employed in reductive carbonylation of nitroarenes and carbonylative Suzuki coupling reactions using formic acid as CO and H2 source. The as-obtained heterogeneous catalyst was characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDAX), thermal gravimetric analysis (TGA), and vibrating sample magnetometer (VSM). The nanocatalyst was reused for 5 cycles with a negligible reduction in the yield of products. All reactions were carried out with high yields and under suitable and safe conditions. Also, we have successfully applied formic acid as a good and safe alternative to CO and H2 gases.
- Jadidi Nejad, Masoumeh,Heydari, Akbar
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- Acylboronates in polarity-reversed generation of acyl palladium(II) intermediates
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We report a catalytic cross-coupling process between aryl (pseudo)halides and boron-based acyl anion equivalents. This mode of acylboronate reactivity represents polarity reversal, which is supported by the observation of tetracoordinated boronate and acyl palladium(II) species by 11B, 31P NMR, and mass spectrometry. A broad scope of aliphatic and aromatic acylboronates has been examined, as well as a variety of aryl (pseudo)halides.
- Trofimova, Alina,Holownia, Aleksandra,Tien, Chieh-Hung,?irvinskas, Martynas J.,Yudin, Andrei K.
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supporting information
p. 3294 - 3299
(2021/05/07)
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- Self-Assembled 2,3-Dicyanopyrazino Phenanthrene Aggregates as a Visible-Light Photocatalyst
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In this study, 2,3-dicyanopyrazino phenanthrene (DCPP), a commodity chemical that can be prepared at an industrial scale, was used as a photocatalyst in lieu of Ru or Ir complexes in C-X (X = C, N, and O) bond-forming reactions under visible-light irradiation. In these reactions, [DCPP]n aggregates were formed in situ through physical π-πstacking of DCPP monomers in organic solvents. These aggregates exhibited excellent photo- and electrochemical properties, including a visible light response (430 nm), long excited-state lifetime (19.3 μs), high excited-state reduction potential (Ered([DCPP]n*/[DCPP]n·-) = +2.10 V vs SCE), and good reduction stability. The applications of [DCPP]n aggregates as a versatile visible-light photocatalyst were demonstrated in decarboxylative C-C cross-coupling, amidation, and esterification reactions.
- He, Min,Yu, Xiaoqiang,Wang, Yi,Li, Fei,Bao, Ming
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p. 5016 - 5025
(2021/04/12)
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- Method for preparing aldehyde ketone compound through olefin oxidation
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The invention provides a method for preparing an aldehyde ketone compound by olefin oxidation, which relates to an olefin oxidative cracking reaction in which oxygen participates. The method comprises the following specific steps: in the presence of a solvent and an oxidant, carrying out oxidative cracking on an olefin raw material to obtain a corresponding aldehyde ketone product. Compared with the traditional method, the method does not need to add any catalyst or ligand, does not need to use high-pressure oxygen, has the advantages of simple and mild reaction conditions, environment friendliness, low cost, high atom economy and the like, is wide in substrate application range and high in yield, and has a wide application prospect in the aspects of synthesis of aldehyde ketone medical intermediates and chemical raw materials.
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Paragraph 0019
(2021/04/07)
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- Poly(ethylene glycol) dimethyl ether mediated oxidative scission of aromatic olefins to carbonyl compounds by molecular oxygen
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A simple, and practical oxidative scission of aromatic olefins to carbonyl compounds using O2as the sole oxidant with poly(ethylene glycol) dimethyl ether as a benign solvent has been developed. A wide range of monosubstituted,gem-disubstituted, 1,2-disubstituted, trisubstituted and tetrasubstituted aromatic olefins was successfully converted into the corresponding aldehydes and ketones in excellent yields even with gram-scale reaction. Some control experiments were also conducted to support a possible reaction pathway.
- Yu, Tao,Guo, Mingqing,Wen, Simiaomiao,Zhao, Rongrong,Wang, Jinlong,Sun, Yanli,Liu, Qixing,Zhou, Haifeng
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p. 13848 - 13852
(2021/04/22)
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- Pd-Catalysed carbonylative Suzuki-Miyaura cross-couplings using Fe(CO)5under mild conditions: generation of a highly active, recyclable and scalable ‘Pd-Fe’ nanocatalyst
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The dual function and role of iron(0) pentacarbonyl [Fe(CO)5] has been identified in gaseous CO-free carbonylative Suzuki-Miyaura cross-couplings, in which Fe(CO)5supplied COin situ, leading to the propagation of catalytically active Pd-Fe nanoparticles. Compared with typical carbonylative reaction conditions, CO gas (at high pressures), specialised exogenous ligands and inert reaction conditions were avoided. Our developed reaction conditions are mild, do not require specialised CO high pressure equipment, and exhibit wide functional group tolerance, giving a library of biaryl ketones in good yields.
- Zhu, Zhuangli,Wang, Zhenhua,Jian, Yajun,Sun, Huaming,Zhang, Guofang,Lynam, Jason M.,McElroy, C. Robert,Burden, Thomas J.,Inight, Rebecca L.,Fairlamb, Ian J. S.,Zhang, Weiqiang,Gao, Ziwei
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supporting information
p. 920 - 926
(2021/02/09)
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- Selective Acylation of Aryl- A nd Heteroarylmagnesium Reagents with Esters in Continuous Flow
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A selective acylation of readily accessible organomagnesium reagents with commercially available esters proceeds at convenient temperatures and short residence times in continuous flow. Flow conditions allow us to prevent premature collapse of the hemiacetal intermediates despite noncryogenic conditions, thus furnishing ketones in good yields. Throughout, the coordinating ability of the ester and/or Grignard was crucial for the reaction outcome. This was leveraged by the obtention of several bisaryl ketones using 2-hydroxy ester derivatives as substrates.
- Heinz, Benjamin,Djukanovic, Dimitrije,Ganiek, Maximilian A.,Martin, Benjamin,Schenkel, Berthold,Knochel, Paul
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p. 493 - 496
(2020/01/31)
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- Water Phase, Room Temperature, Ligand-Free Suzuki–Miyaura Cross-Coupling: A Green Gateway to Aryl Ketones by C–N Bond Cleavage
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We report herein a green strategy for synthesis of aryl ketones from twisted amides by using Pd(OAc)2 as catalysts. This method shows high functional group tolerance to offer a variety of ketones in good yields under mild conditions (up to 94 %). Notably, this methodology demonstrates the first water phase, room temperature, ligand-free Suzuki–Miyaura coupling through C–N bond cleavage, which is environmentally friendly and might facilitate the development of amide based green chemistry.
- Zhang, Yuqi,Wang, Zijia,Tang, Zhao,Luo, Zhongfeng,Wu, Hongxiang,Liu, Tingting,Zhu, Yulin,Zeng, Zhuo
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p. 1620 - 1628
(2020/03/04)
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- Carbonylative Suzuki-Miyaura cross-coupling by immobilized Ni?Pd NPs supported on carbon nanotubes
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In this study, a novel carbon nanotube (CNT) based nanocatalyst (Ni?Pd/CNT) was synthesized by modifying CNTs using Ni?Pd core-shell nanoparticles (NPs). Ni?Pd/CNT was used in catalytic carbonylative cross-coupling between 4-iodoanisole and phenylboronic acid. The Ni?Pd NPs possessed a magnetic nickel (Ni) core with a palladium (Pd) structural composite shell. Thus, the use of Ni had led to a reduced consumption of Pd without sacrificing the overall catalytic performance, simultaneously making it reusable as it could be conveniently recovered from the reaction mixture by using an external magnetic field. Immobilization of the Ni?Pd NPs on carbon nanotubes not only prevented their aggregation, but also significantly enhanced the accessibility of the catalytically active sites. The abovementioned approach based on carbon nanotubes and Ni?Pd NPs provided a useful platform for the fabrication of noble-metal-based nanocatalysts with easy accessibility and low cost, which may allow for an efficient green alternative for various catalytic reductions. This journal is
- Dujuan, Ouyang,Jixiang, Li,Mustapha, Mazli,Nan, Liu,Rouhi, Jalal,Wenhui, Duan,Yalan, Cai
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p. 27923 - 27931
(2020/11/07)
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- Asymmetric Transfer Hydrogenation of o-Hydroxyphenyl Ketones: Utilizing Directing Effects That Optimize the Asymmetric Synthesis of Challenging Alcohols
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A systematic range of o-hydroxyphenyl ketones were reduced under asymmetric transfer hydrogenation conditions using the C3-tethered catalyst 2. Two directing effects, i.e., an o-hydroxyphenyl coupled to a bulky aromatic on the opposite side of the ketone substrate, combine in a matched manner to deliver reduction products with very high enantiomeric excess.
- Clarkson, Guy J.,Wills, Martin,Zheng, Ye
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supporting information
(2020/05/05)
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- Photo-induced phosphorus radical involved semipinacol rearrangement reaction: Highly synthesis of γ-oxo-phosphonates
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Hydroxyphosphoric acids display the unique biological activities, and they have some attractive prospects as clinical drug moleculars. Herein, a new approach for the synthesis of γ-oxo-phosphonates (the precursor of hydroxyphosphoric acid) has been established through the semipinacol rearrangement tactic involved the photo-induced phosphorus radical process. Most important, this transformation is avoid of the external oxidants, and occurs very well under the sunlight irradiation, meanwhile the γ-oxo-phosphonate was easily derivatized to obtain γ-hydroxyphosphoric acid, thus highlights the synthesis value of this method.
- Wang, Chunhai,Huang, Xiaoling,Liu, Xueting,Gao, Suqian,Zhao, Bin,Yang, Shangdong
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supporting information
p. 677 - 680
(2019/08/27)
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- Palladium-Catalyzed Suzuki Coupling of N-Acyloxazolidinones via Selective Cleavage of C–N Bonds
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By implementing a palladium-catalyzed Suzuki coupling reaction of N-acyloxazolidinones with arylboronic acid, we herein report on the preparation of substituted diaryl ketones via selective cleavage of exocyclic C–N Bonds. The reaction was carried out under mild reaction conditions with excellent functional group compatibility in good yields (up to 93 %).
- Jian, Junsheng,He, Zhanyu,Zhang, Yuqi,Liu, Tingting,Liu, Lizhen,Wang, Zijia,Wang, Hui,Wang, Sanyong,Zeng, Zhuo
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supporting information
p. 4176 - 4180
(2020/07/13)
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- Palladium-Catalyzed Amide N-C Hiyama Cross-Coupling: Synthesis of Ketones
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N-Acylglutarimides and arylsiloxanes reacted in the presence of Pd(OAc)2/PCy3, Et3N·3HF, and LiOAc to provide the corresponding arylketones in good yields. Aryl-, vinyl-, and alkyl-substituted N-acylglutarimides showed good activity in the coupling reactions of arylsiloxanes. The reaction had a broad substrate scope and showed good functional group tolerance. N-Benzoylsuccinimide and N-protected N-phenylbenzamides showed good activities in coupling reactions with phenylsiloxane. The employment of CuF2 as an activor afforded the decarbonylative products at 160 °C.
- Idris, Muhammad Aliyu,Lee, Sunwoo
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supporting information
p. 9190 - 9195
(2020/11/18)
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- Chemoselective Synthesis of Aryl Ketones from Amides and Grignard Reagents via C(O)-N Bond Cleavage under Catalyst-Free Conditions
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Conversion of a wide range of N-Boc amides to aryl ketones was achieved with Grignard reagents via chemoselective C(O)-N bond cleavage. The reactions proceeded under catalyst-free conditions with different aryl, alkyl, and alkynyl Grignard reagents. α-Ketoamide was successfully converted to aryl diketones, while α,β-unsaturated amide underwent 1,4-addition followed by C(O)-N bond cleavage to provide diaryl propiophenones. N-Boc amides displayed higher reactivity than Weinreb amides with Grignard reagents. A broad substrate scope, excellent yields, and quick conversion are important features of this methodology.
- Sureshbabu, Popuri,Azeez, Sadaf,Muniyappan, Nalluchamy,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
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p. 11823 - 11838
(2019/10/02)
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- Carbonylative Suzuki coupling and alkoxycarbonylation of aryl halides using palladium supported on phosphorus-doped porous organic polymer as an active and robust catalyst
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Developing highly active catalysts with the combined advantages of molecular and solid catalysis is considered as the “Holy Grail” in the area of catalysis research. Herein, a phosphorus-doped porous polymer-immobilized palladium was successfully developed as an efficient, robust, and recyclable catalyst for the carbonylative Suzuki coupling and alkoxycarbonylation reactions of aryl halides. Rather than just as an immobilizing molecular catalyst, palladium supported on phosphorus-doped porous organic polymer exhibits even better catalytic performances than that of its analogue homogeneous catalysts in both carbonylation reactions. Moreover, the catalyst can be easily separated and reused for at least 5 times without significant loss in reactivity. Importantly, the catalyst was highly stable under carbonylation reaction conditions, and no palladium nanoparticle was observed even after the 5th reuse.
- Wan, Yali,Song, Fangxiang,Ye, Tao,Li, Guangxing,Liu, Dingfu,Lei, Yizhu
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- Sodium Methyl Carbonate as an Effective C1 Synthon. Synthesis of Carboxylic Acids, Benzophenones, and Unsymmetrical Ketones
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Reported is the synthesis of carboxylic acids, symmetrical ketones, and unsymmetrical ketones with selectivity achieved by exploiting the differential reactivity of sodium methyl carbonate with Grignard and organolithium reagents.
- Hurst, Timothy E.,Deichert, Julie A.,Kapeniak, Lucas,Lee, Roland,Harris, Jesse,Jessop, Philip G.,Snieckus, Victor
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supporting information
p. 3882 - 3885
(2019/06/07)
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- Ligand-free Palladium-Catalyzed Carbonylative Suzuki Coupling of Aryl Iodides in Aqueous CH3CN with Sub-stoichiometric Amount of Mo(CO)6 as CO Source
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A new method for the synthesis of diaryl and heterodiaryl ketones has been established based on the palladium-catalyzed carbonylative Suzuki coupling approach with sub-stoichiometric Mo(CO)6 as CO source. Using 0.5 mol% of Pd(TFA)2 as catalyst, 0.5 equivalent of Mo(CO)6 as solid carbonyl reagent and 3 equivalent of K3PO4 as base, a wide range of functionalized (hetero)aryl iodides and (hetero)aryl boronic acids could smoothly proceed the carbonylative cross-coupling reaction in aqueous CH3CN at 50 °C, affording the corresponding ketones in good to excellent yields. The newly developed method was easy to operate under mild conditions with high efficiency. (Figure presented.).
- Sun, Nan,Sun, Qingxia,Zhao, Wei,Jin, Liqun,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
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p. 2117 - 2123
(2019/03/28)
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- Sequential Organozinc Formation and Negishi Cross-Coupling of Amides Catalysed by Cobalt Salt
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Herein, a cobalt-catalysed Negishi-type cross-coupling of amide derivatives is described. Apart from being the first example of cobalt-catalysed Negishi-type coupling of amides, the process described employs a unique, simple, and cheap catalytic system to perform both the organozinc formation and the Negishi-type coupling. Indeed, the same cobalt(II) bromide salt used to form the arylzinc species from aryl bromides is then re-used to perform the cross coupling of this resulting arylzinc with N-benzoyl glutarimides at room temperature. The main advantages of the reaction presented are its robustness and ease of use. Indeed, the reactions of organozinc formation and Negishi-type coupling are performed without precautions toward water or oxygen. (Figure presented.).
- Dorval, Céline,Dubois, Elodie,Bourne-Branchu, Yann,Gosmini, Corinne,Danoun, Grégory
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supporting information
p. 1777 - 1780
(2019/02/26)
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- Synthesis of Functionalized Ketones from Acid Chlorides and Organolithiums by Extremely Fast Micromixing
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Synthesis of ketones containing various functional groups from acid chlorides bearing electrophilic functional groups and functionalized organolithiums was achieved using a flow microreactor system. Extremely fast mixing is important for high chemoselectivity.
- Nagaki, Aiichiro,Sasatsuki, Kengo,Ishiuchi, Satoshi,Miuchi, Nobuyuki,Takumi, Masahiro,Yoshida, Jun-ichi
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supporting information
p. 4946 - 4950
(2019/03/21)
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- Alkali Metal Effects in Trans-Metal-Trapping (TMT): Comparing LiTMP with NaTMP in Cooperative MTMP/Ga(CH2SiMe3)3 Metalation Reactions
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Stepwise metalation and trapping, so called trans-metal-trapping (TMT), of anisole is studied using LiTMP as base and Ga(CH2 SiMe3)3 as trap. The isolated 'trapped' intermediate is also assessed in C-C bond forming reactions, highlighting the inherent advantages and remaining challenges of this system. The same base trap mixture is found to metallate N-Me bonds of the diamines TMEDA and PMDETA. Comparative studies replacing LiTMP by NaTMP have found significant alkali metal effects on the extent of both base-trap cocomplexation and onward reactivities of TMT products.
- McLellan, Ross,Uzelac, Marina,Bole, Leonie J.,Gil-Negrete, Jose María,Armstrong, David R.,Kennedy, Alan R.,Mulvey, Robert E.,Hevia, Eva
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p. 1207 - 1215
(2019/02/26)
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- Transition-metal-free carbonylation of aryl halides with arylboronic acids by utilizing stoichiometric CHCl3 as the carbon monoxide-precursor
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Under transition-metal-free conditions, carbonylative Suzuki couplings of aryl halides with arylboronic acid using stoichiometric CHCl3 as the carbonyl source has been developed. The simple, efficient, and environmentally benign method was successfully applied to the synthesis of Fenofibric acid, naphthyl phenstatin, and carbon-13 labeled biaryl ketone.
- Xu, Fangning,Li, Dan,Han, Wei
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supporting information
p. 2911 - 2915
(2019/06/18)
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- Highly efficient synthesis of aryl ketones by PEPPSI-palladium catalyzed acylative Suzuki coupling of amides with diarylborinic acids
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An improved acylative cross-coupling of various N-methyl-N-tosyl amides with diarylborinic acids for synthesis of aryl ketones is developed. In most cases, aryl ketones could be obtained in excellent yields by using 1 mol% 2,6-diisopropylphenylimidazolylidene and 3-chloropyridine co-supported palladium chloride as catalyst in the presence of 3 equiv. K2CO3 as base in refluxing THF. The readily prepared and cost-effective substrates, N-methyl-N-tosylamides and diarylborinic acids, and the commercially available catalyst system promise a practical and efficient access to aryl ketones.
- Wang, Chen,Huang, Lingyun,Wang, Fengze,Zou, Gang
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p. 2299 - 2301
(2018/05/16)
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- Introducing Glycerol as a Sustainable Solvent to Organolithium Chemistry: Ultrafast Chemoselective Addition of Aryllithium Reagents to Nitriles under Air and at Ambient Temperature
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Edging closer towards developing air and moisture compatible polar organometallic chemistry, the chemoselective and ultrafast addition of a range of aryllithium reagents to nitriles has been accomplished by using glycerol as a solvent, at ambient temperature in the presence of air, establishing a novel sustainable access to aromatic ketones. Addition reactions occur heterogeneously (“on glycerol conditions”), where the lack of solubility of the nitriles in glycerol and the ability of the latter to form strong intermolecular hydrogen bonds seem key to favouring nucleophilic addition over competitive hydrolysis. Remarkably, PhLi exhibits a greater resistance to hydrolysis working “on glycerol” conditions than “on water”. Introducing glycerol as a new solvent in organolithium chemistry unlocks a myriad of opportunities for developing more sustainable, air and moisture tolerant main-group-metal-mediated organic synthesis.
- Rodríguez-álvarez, María J.,García-álvarez, Joaquín,Uzelac, Marina,Fairley, Michael,O'Hara, Charles T.,Hevia, Eva
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p. 1720 - 1725
(2018/01/27)
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- A porous Br?nsted superacid as an efficient and durable solid catalyst
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The development of catalysts able to assist industrial chemical transformations is a topic of high importance. In view of the versatile catalytic capabilities of acid catalysts, extensive research efforts are being made to develop porous superacid materials with a high density of accessible active sites to replace molecular acid catalysts. Herein, we report the rational development of a porous Br?nsted superacid by combining important elements that target high strength acidity into one material, as demonstrated by grafting the sulfonic acid group onto a highly fluorinated porous framework, where the acid strength and stability are greatly enhanced by an electron-withdrawing environment provided by the polymer backbone, reminiscent of that seen in Nafion resin. In addition, the densely arranged acid groups that are confined in the three-dimensional nanospace facilitate the transfer of hydrons, thereby further increasing the acidity. By virtue of the pore structure and strong acidity, this system exhibits excellent performance for a wide range of reactions, far outperforming commercial acid resins under repeated batch and flow reaction conditions. Our findings demonstrate how this synthetic approach may instruct the future design of heterogeneous acid catalysts with advantageous reaction capabilities and stability.
- Sun, Qi,Hu, Kewei,Leng, Kunyue,Yi, Xianfeng,Aguila, Briana,Sun, Yinyong,Zheng, Anmin,Meng, Xiangju,Ma, Shengqian,Xiao, Feng-Shou
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supporting information
p. 18712 - 18719
(2018/10/15)
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- Ni/Ti Dual Catalytic Cross-Coupling of Nitriles and Organobromides to Access Ketones
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Herein, we report the development of a dual catalytic approach for the cross-coupling of nitriles with aryl- and aliphatic-bromides. A titanium(III) catalyst is used to activate nitriles enabling their coupling with organobromides through a nickel catalyst. The Ni/Ti system efficiently prepared unsymmetrical ketones with good chemoselectivity and could selectively couple a bromide in the presence of other functionalizable handles.
- Chenniappan, Vinoth Kumar,Silwal, Sajan,Rahaim, Ronald J.
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p. 4539 - 4544
(2018/05/23)
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- Diaryl vinyl cyclic amine derivatives and preparation method thereof
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The invention provides diaryl vinyl cyclic amine derivatives and a preparation method thereof. The aryl substituted groups of the diaryl vinyl cyclic amine derivatives have a hydroxyl or hydroxy derivative functional groups in the ortho positions of vinyl groups. The bioactivity test shows that the compounds have anticholinergic activity, and the ortho-hydroxy groups can significantly enhance theantagonistic activity; the compounds can be used as active pharmaceutical ingredients for treating asthma, chronic obstructive pulmonary disease (COPD), rhinorrhea caused by allergic rhinitis and cold, urinary incontinence, Parkinson's disease, and the like.
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Paragraph 0377; 0379-0382
(2018/09/08)
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- The cytochrome: C -cyclo[6]aramide complex as a supramolecular catalyst in methanol
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A hydrogen-bonded macrocycle, cyclo[6]aramide, was found to form a supramolecular complex with cytochrome c, which enables the solubilization of the heme protein in methanol. The supramolecular complexation was evidenced by UV-vis, CD, and Raman spectroscopic techniques via structural characterization. Computational simulation based on the DFT method reveals the presence of strong hydrogen bonds formed between the lysine residues exposed on the protein surface and the oxygen atoms residing in the cavity of cyclo[6]aramide apart from cation-π interactions. The resulting cytochrome c-cyclo[6]aramide 1 exhibited higher activities than unmodified cytochrome c in the oxidation of benzhydrol to benzophenone with hydrogen peroxide at low temperatures. The enhanced activity with lowering temperature up to -40 °C indicates that the complex can act as a "cold-active" synzyme. The results achieved here demonstrate the potential of hydrogen-bonded macrocycles in supramolecular chemistry for catalytic reactions via ligand-protein interactions.
- Pan, Wang,Mao, Lijun,Shi, Mingsong,Fu, Yonghong,Jiang, Xiaomin,Feng, Wen,He, Youzhou,Xu, Dingguo,Yuan, Lihua
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supporting information
p. 3857 - 3866
(2018/03/06)
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- N-heterocyclic carbene palladium(II)-catalyzed Suzuki-Miyaura cross coupling of N-acylsuccinimides by C-N cleavage
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An easily prepared, well-defined N-heterocyclic carbene-palladium(II) complex was found to be an efficient catalyst for the Suzuki-Miyaura cross-coupling of N-acylsuccinimides with arylboronic acids via C-N bond activation. Under the optimal conditions, a
- Guo, Han,Guo, Jiarui,Jia, Dingli,Liu, Lantao,Wang, Hengjin,Wang, Tao,Zhang, Wen
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- Pd-NHC catalysed Carbonylative Suzuki coupling reaction and its application towards the synthesis of biologically active 3-aroylquinolin-4 (1H)-one and acridone scaffolds
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We have unfolded a convenient and mild protocol for the synthesis of diaryl ketones via Pd- NHC catalysed carbonylative Suzuki coupling reaction. Notably, this method offers advantages like no use of toxic CO gas, shorter reaction time, high yield, and broad substrate scope. Several sensitive functional groups (like-COMe, -COOMe, -F, -Cl, -Br, -NH2, -CN) are well tolerated in this reaction. In addition, we have also demonstrated a new efficient route for the synthesis of biologically active and pharmaceutically important 2-substituted 3-Aroylquinolin-4(1H)-ones and acridone scaffolds.
- Ghosh, Prasanjit,Ganguly, Bhaskar,Das, Sajal
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- N-Acyl-5,5-dimethylhydantoin, a New Mild Acyl-Transfer Reagent in Pd Catalysis: Highly Efficient Synthesis of Functionalized Ketones
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The palladium-catalyzed Suzuki-Miyaura cross-coupling of N-acyl-5,5-dimethylhydantoins with arylboronic acids has been developed via selective amides C-N bond cleavage. The new reagent is commercially available and air-/moisture-stable, and it offers a variety of ketones in good yields through Suzuki coupling under mild conditions (up to 95%).
- Luo, Zhongfeng,Liu, Tingting,Guo, Weijie,Wang, Zijia,Huang, Jingjun,Zhu, Yulin,Zeng, Zhuo
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p. 1188 - 1199
(2018/09/06)
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- MeZnOMe-mediated reaction of aldehydes with Grignard reagents: A glance into nucleophilic addition/Oppenauer oxidation pathway
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A novel organozincate of RMgX ?MeZnOMe ?LiCl type, formed in situ via transmetalation of Grignard reagent RMgBr ?LiCl with MeZnOMe, is shown to be an excellent organometallic species in the nucleophilic addition/Oppenauer oxidation of aldehydes to generate aromatic ketones in high yield. This transformation allows quick access to structurally diverse aryl, heteroaryl, benzyl and alkyl ketones with broad substrate scope and excellent functional group tolerance.
- Fu, Ying,Ma, Xian-Zhen,Shi, Chun-Zhao,Shen, Tong,Du, Zhengyin
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- Pd-PEPPSI: Water-Assisted Suzuki?Miyaura Cross-Coupling of Aryl Esters at Room Temperature using a Practical Palladium-NHC (NHC=N-Heterocyclic Carbene) Precatalyst
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A Pd-PEPPSI-catalyzed (Pd=Palladium, PEPPSI=pyridine-enhanced precatalyst preparation stabilization and initiation) Suzuki-Miyaura cross-coupling of aryl esters via selective C?O cleavage at room temperature is reported. The developed catalyst system displays broad substrate scope with respect to both components under practical ambient reaction conditions using readily-available, cheap, modular, air- and moisture-stable Pd-NHC precatalyst (NHC=N-heterocyclic carbene). The use of water proved crucial for achieving high reactivity in this coupling. The catalyst system represents the mildest conditions for the Suzuki?Miyaura cross-coupling of aryl esters reported to date. The protocol also allowed for achieving TON >1,000 (TON=turnover number) in the Suzuki?Miyaura ester coupling for the first time. (Figure presented.).
- Li, Guangchen,Shi, Shicheng,Lei, Peng,Szostak, Michal
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supporting information
p. 1538 - 1543
(2018/03/01)
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- Rapidly Activating Pd-Precatalyst for Suzuki-Miyaura and Buchwald-Hartwig Couplings of Aryl Esters
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Esters are valuable electrophiles for cross-coupling due to their ubiquity and ease of synthesis. However, harsh conditions are traditionally required for the effective cross-coupling of ester substrates. Utilizing a recently discovered precatalyst, Pd-catalyzed Suzuki-Miyaura and Buchwald-Hartwig reactions involving cleavage of the C(acyl)-O bond of aryl esters that proceed under mild conditions are reported. The Pd(II) precatalyst is highly active because it is reduced to the Pd(0) active species more rapidly than previous precatalysts.
- Dardir, Amira H.,Melvin, Patrick R.,Davis, Ryan. M.,Hazari, Nilay,Mohadjer Beromi, Megan
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supporting information
p. 469 - 477
(2018/02/19)
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- Suzuki-Miyaura Cross-Coupling of N-Acylpyrroles and Pyrazoles: Planar, Electronically Activated Amides in Catalytic N-C Cleavage
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The formation of C-C bonds from amides by catalytic activation of the amide bond has been thus far possible by steric distortion. Herein, we report the first example of a general Pd-catalyzed Suzuki-Miyaura cross-coupling of planar amides enabled by the combination of (i) electronic-activation of the amide nitrogen in N-acylpyrroles and pyrazoles and (ii) the use of a versatile Pd-NHC catalysis platform. The origin and selectivity of forming acylmetals, including the role of twist, are discussed.
- Meng, Guangrong,Szostak, Roman,Szostak, Michal
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p. 3596 - 3599
(2017/07/15)
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- N-Methylamino Pyrimidyl Amides (MAPA): Highly Reactive, Electronically-Activated Amides in Catalytic N-C(O) Cleavage
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Despite recent progress in catalytic cross-coupling technologies, the direct activation of N-alkyl-N-aryl amides has been a challenging transformation. Here, we report the first Suzuki cross-coupling of N-methylamino pyrimidyl amides (MAPA) enabled by the controlled nN → πAr conjugation and the resulting remodeling of the partial double bond character of the amide bond. The new mode of amide activation is suitable for generating acyl-metal intermediates from unactivated primary and secondary amides.
- Meng, Guangrong,Lalancette, Roger,Szostak, Roman,Szostak, Michal
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p. 4656 - 4659
(2017/09/12)
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- N-Acylsuccinimides: Efficient acylative coupling reagents in palladium-catalyzed Suzuki coupling via C–N cleavage
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An acylative Suzuki coupling of activated amides with aryl boronic acids has been reported via palladium-catalyzed C–N bond cleavage. This protocol demonstrate amides can be activated by an atom-economic and cheap succinimide, which can be efficiently utilized to synthesize broad array of diaryl ketones in moderate to good yields.
- Cui, Ming,Chen, Zeyu,Liu, Tingting,Wang, Hui,Zeng, Zhuo
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p. 3819 - 3822
(2017/09/15)
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- Ni-Catalyzed cross-coupling reactions of N-acylpyrrole-type amides with organoboron reagents
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The catalytic conversion of amides to ketones is highly desirable yet challenging in organic synthesis. We herein report the first Ni/bis-NHC-catalyzed cross-coupling of N-acylpyrrole-type amides with arylboronic esters to obtain diarylketones. This method is facilitated by a new chelating bis-NHC ligand. The reaction tolerates diverse functional groups on both arylamide and arylboronic ester partners including sensitive ester and ketone groups.
- Huang, Pei-Qiang,Chen, Hang
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p. 12584 - 12587
(2017/11/30)
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- Synthesis and structural characterization of Pd(II) thiosemicarbazonato complex: Catalytic evaluation in synthesis of diaryl ketones from aryl aldehydes and arylboronic acids
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A simple route to synthesize triphenylphosphinopalladium(II) thiosemicarbazonato complex has been described. Elemental analysis, spectral (IR, NMR) and single crystal X-ray diffraction techniques were employed for the complete characterization of the complex. The latter was found to be effective catalyst for carbon–carbon cross-coupling reaction of aryl- and heteroarylboronic acids with aromatic and heteroaromatic aldehydes to form the corresponding diaryl ketones. The influence of reaction parameters such as solvent, base, reaction temperature and catalyst loading was also investigated.
- Prabhu, Rupesh Narayana,Ramesh, Rengan
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supporting information
p. 405 - 409
(2017/01/10)
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- KCC-1/GMSI/VB12 as a new nano catalyst for the carbonylative Suzuki-Miyaura crosscoupling reaction
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In this study, vitamin B12 (VB12) modified with a (3-glycidyloxypropyl)trimethoxysilane (GMSI) moiety grafted onto KCC-1 (KCC-1/GMSI/VB12) was prepared for the first time. Its capability was evaluated for the carbonylative Suzuki-Miyaura crosscoupling reaction between carbon monoxide, 4-iodoanisole and phenylboronic acid, affording the desired products in high yield. Applying 1 mg of catalyst and 1 mmol of K2CO3 as base in 10 mL anisole and heating under reflux for 1 h are the best conditions for the reaction. The catalysts were very active in catalytic recycling experiments over ten catalytic cycles.
- Sadeghzadeh, Seyed Mohsen,Zhiani, Rahele,Emrani, Shokufe
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p. 32139 - 32145
(2017/07/11)
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- Carbonylative Suzuki Coupling Reaction Catalyzed by a Hydrospirophosphorane Palladium Complex
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A Pd complex with the H-spirophosphorane ligand, PdCl2{P(OCMe2CMe2O)OC6H4NH2} (Cat. 1), was used as the catalyst in the carbonylative Suzuki coupling of substituted iodobenzenes with arylboronic acids and with sodium tetraphenylborate. Substituted diarylketones were obtained in good to excellent yields and a selectivity over 95 % under 1 atm of CO with 1.5 mol % of the catalyst. The promoting role of the H-spirophosphorane ligand in the catalytic process was evidenced. We used X-ray photoelectron spectroscopy, TEM, and 31P NMR spectroscopy to reveal that during the reaction Cat. 1 undergoes transformation into Pd complexes that bear the spirophosphorane ligand or other P ligands formed by its dealkylation and to Pd nanoparticles. All these Pd species contribute to the high productivity of the system.
- Wójcik, Przemys?aw,Sygellou, Labrini,Gniewek, Andrzej,Skar?yńska, Anna,Trzeciak, Anna
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p. 4397 - 4409
(2017/11/21)
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- Carbonylative Suzuki cross-coupling reaction catalyzed by bimetallic Pd-Pt nanodendrites under ambient CO pressure
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Pd-catalyzed reactions between aryl boronic acids and aryl halides have undergone rapid development since the pioneering work of Suzuki and co-workers in 1979. In this paper, we described a high-efficient and cost-effective bimetallic Pd-Pt nanodendrites catalyst based on a ligand-free strategy to synthesize diaryl ketones via CO direct insertion to boronic acids and aryl halides. A variety of aryl boronic acids and aryl halides were investigated, which showed great functional group tolerance and versatile aryl ketone products in high yield.
- Wang, Zheng-Jun,Wang, Xue-Yan,Wang, Xia,Liang, Zhi-Wu,Xu, Xinhua
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- A kind of alkali to promote self-oxidation of diaryl alkane preparation diarylketones method (by machine translation)
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The invention discloses a kind of alkali to promote self-oxidation of diaryl alkane preparation diarylketones method. The method is that the diaryl paraffins compound is dissolved in an organic solvent in the drying of, the addition of a base, in the 25 - 80o C reaction under air or oxygen atmosphere for 0.5 - 5 hours, to obtain diarylketones; said two aryl paraffins compound and alkali molar ratio of 1:1 - 1:3. The method overcomes the need in the prior art strong acid or expensive metal reagent or a strong oxidizing agent and the like, has the following advantages: 1) to oxygen as the oxidizing agent, avoids the use of strong or expensive chemical oxidizing agent; 2) transition metal-free catalyst, avoids the heavy metal ion in the product; 3) the process is simple, low cost, wide range of the substrate, friendly to the environment. The synthesis method disclosed in this invention in the preparation of diarylketones industrialization of the play an important role in the production. (by machine translation)
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Paragraph 0019
(2017/08/28)
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- Synthesis of Benzodihydrofurans by Asymmetric C?H Insertion Reactions of Donor/Donor Rhodium Carbenes
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Metal carbenes appended with two electron-donating groups, known as “donor/donor” carbenes, undergo diastereo- and enantioselective rhodium-catalyzed C?H insertion reactions with ether substrates to form benzodihydrofurans. Unlike the reactions of metal carbenes with electron-withdrawing groups attached, the attenuated electrophilicity enables these reactions to be conducted in Lewis basic solvents (e.g., acetonitrile) and in the presence of water. The diazo precursors for these species are prepared in situ from hydrazone using a mild and chemoselective oxidant (MnO2). Although this sequence often can be performed in one-pot, control experiments have elucidated why a “two-pot” process is often more efficient. A thorough screening of achiral catalysts demonstrated that sterically encumbered catalysts are optimal for diastereoselective reactions. Although efficient insertion into allylic and propargylic C?H bonds is observed, competing dipolar cycloaddition processes are noted for some substrates. The full substrate scope of this useful method of benzodihydrofuran synthesis, mechanisms of side reactions, and computational support for the origins of stereoselectivity are described.
- Lamb, Kellan N.,Squitieri, Richard A.,Chintala, Srinivasa R.,Kwong, Ada J.,Balmond, Edward I.,Soldi, Cristian,Dmitrenko, Olga,Casti?eira Reis, Marta,Chung, Ryan,Addison, J. Bennett,Fettinger, James C.,Hein, Jason E.,Tantillo, Dean J.,Fox, Joseph M.,Shaw, Jared T.
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supporting information
p. 11843 - 11855
(2017/09/07)
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- General Method for the Suzuki-Miyaura Cross-Coupling of Primary Amide-Derived Electrophiles Enabled by [Pd(NHC)(cin)Cl] at Room Temperature
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A general, highly selective method for the room temperature Suzuki-Miyaura cross-coupling of commonly encountered primary benzamides is reported. A combination of site-selective N,N-di-Boc-activation (tert-butoxycarbonyl activation) of the amide nitrogen with practical air- and moisture-stable, well-defined, and highly reactive [Pd(NHC)(cin)Cl] (NHC = N-heterocyclic carbene; cin = cinnamyl) provides a highly effective route to biaryl ketones from primary amides in high yields. For the first time, a TON of >1000 has been achieved in amide acyl cross-coupling.
- Lei, Peng,Meng, Guangrong,Ling, Yun,An, Jie,Nolan, Steven P.,Szostak, Michal
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p. 6510 - 6513
(2017/12/26)
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