- Mass Spectral and Pyrolitic Studies of Some 4,4-Disubstituted 1,4-Dihydro-2H-3,1-benzoxazin-2-ones
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Pyrolysis of 4,4-diaryl-1,4-dihydro-2H-3,1-benzoxazin-2-ones at 230-240 deg C gives 9-arylacridines and (2-aminophenyl)diarylmethanes.Their formation correlates well with the mass fragmentation of the respective parent compounds.
- Acharya, Baman Prasad,Misra, Bijaya Kumar,Rao, Yerramalli Ramachandra
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- 2-(2,1-Benzoxazol-3-yl)-3,5-dimethoxyphenol and 3-phenyl-2,1-benzoxazole
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The title compounds, C15H13NO4, (I), and C13H9NO, (II), are produced, along with the corresponding anilines, by the reduction of the appropriate o-nitrobenzophenones. In (I), the planar benzisoxazole and phenol fragments are tilted relative to one another by a rotation of 53.02 (14)° about the bond joining them, and the molecules are linked into chains by phenol O-H...N and phenyl C-H...O oxazole hydrogen bonds. The cell of (II) (space group 12/c) contains eight molecules in general positions, four more in the 2b sites, with twofold axial symmetry that induces a degree of disorder, and a further four as centrosymmetric pairs of complete molecules, each with an occupancy of one-half. The relative tilt of the planar fragments varies slightly from one molecule to another but is much less than that in (I), ranging from 8.8 (8) to 12.58 (15)°.
- Howie,Jabbar, Abdul,Lewis, John R.,Nizami, Shaikh S.,Ritchie, Craig F.
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- One-Pot Synthesis of 2-Aminobenzophenones from 2-Alkynyl Arylazides Catalyzed by Pd and Cu Precursors
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We describe a novel one-pot three-step reaction of 2-alkynyl arylazides through palladium-catalyzed formation of 3-hydroxy-3-phenylindolin-2-ones followed by hydrolysis of amide bonds and copper-catalyzed decarboxylation to give 2-aminobenzophenones. This synthetic method works well with various 2-alkynyl arylazides and affords the products in moderate to good yields under mild reaction conditions.
- Fan, Hui,Xu, Shijie,Yang, Fan,Zhang, Xiaoxiang,Zhao, Xuechun
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supporting information
p. 4555 - 4558
(2021/08/30)
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- Metal-Free Synthesis of Alkenylazaarenes and 2-Aminoquinolines through Base-Mediated Aerobic Oxidative Dehydrogenation of Benzyl Alcohols
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A metal-free, base-mediated, and atom-efficient oxidative dehydrogenative coupling of substituted phenylmethanols (benzyl alcohols) with methyl azaarenes or phenylacetonitriles to afford substituted alkenylazaarenes or 2-aminoquinolines, respectively is described. CsOH.H2O was discovered to be the base of choice for obtaining optimal yields of the title compounds, although the reaction could proceed with KOH as well. The protocol that works efficiently in the presence of air is amenable over broad range of substrates.
- Batra, Sanjay,Dahatonde, Dipak J.,Ghosh, Aritra
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p. 2746 - 2751
(2021/06/25)
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- Binuclear Palladium Complex Immobilized on Mesoporous SBA-16: Efficient Heterogeneous Catalyst for the Carbonylative Suzuki Coupling Reaction of Aryl Iodides and Arylboronic Acids Using Cr(CO)6 as Carbonyl Source
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Abstract: In this study, a binuclear palladium complex immobilized on the organo-functionalized SBA-16 was prepared and structurally characterized by routine techniques. Characterizations indicated that the mesostructure of SBA-16 was maintained after the immobilization of palladium complex. Then, the prepared nanomaterial was applied as a heterogeneous catalyst in the carbonylative Suzuki coupling reaction of aryl iodides with arylboronic acids using Cr(CO)6 as carbonyl source. The catalyst was efficiently promoted the coupling reactions of various aryl iodides and arylboronic acids to give the corresponding diaryl ketones in excellent yields. Moreover, the catalyst was readily recovered by filtration and could be reused for seven cycles without losing its structural integrity and catalytic activity. Graphic Abstract: [Figure not available: see fulltext.].
- Niakan, Mahsa,Asadi, Zahra,Emami, Mohammad
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p. 404 - 418
(2020/01/03)
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- Metal-Free, Visible-Light-Enabled Direct C3-H Arylation of Anthranils
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An eosin Y disodium salt-catalyzed photoredox C-H arylation of anthranils is reported. A variety of aryl diazonium tetrafluoroborates were used as aryl sources, providing the C3 cross-coupled products. The in situ generated reactive radicals were trapped by anthranils, providing an alternative method to transition-metal-catalyzed C-H arylations of anthranils. Gold-catalyzed downstream transformations demonstrate the synthetic potential of these valuable building blocks.
- Adak, Tapas,Hashmi, A. Stephen K.,Hu, Chao,Li, Jun,Rudolph, Matthias
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- One-Pot Synthesis of Spirocyclopenta[ a]indene Derivatives via a Cascade Ring Expansion and Intramolecular Friedel-Crafts-Type Cyclization
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A one-pot efficient synthetic approach for the rapid construction of spirocyclopenta[a]indene derivatives has been developed via an iodine-initiated cascade ring expansion and intramolecular Friedel-Crafts-type cyclization from propargyl alcohol-tethered alkylidenecyclobutanes under mild conditions with broad substrate scope. This cascade process can be elegantly conducted on a gram scale. A plausible reaction mechanism has been proposed on the basis of a series of deuterium labeling and control experiments.
- Li, Quanzhe,Liu, Jiaxin,Wei, Yin,Shi, Min
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p. 2438 - 2455
(2020/01/31)
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- Visible Light Induced Cyclization to Spirobi[indene] Skeletons from Functionalized Alkylidienecyclopropanes
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In this paper, we revealed a metal-free and visible light photoinduced method for the rapid construction of spirobi[indene] skeletons, providing a simple and efficient way for easy access to spirobi[indene] scaffolds under mild conditions along with a broad substrate scope and good functional group tolerance.
- Li, Quanzhe,Liu, Jiaxin,Shi, Min,Wei, Yin
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- Rapid construction of cyclopenta[: B] naphthalene frameworks from propargylic alcohol tethered methylenecyclopropanes
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We have developed a new synthetic methodology for the rapid construction of cyclopenta[b]naphthalene frameworks from the reaction of propargylic alcohol tethered methylenecyclopropanes with mesyl chloride in the presence of triethylamine through cascade cyclization. The reaction can be performed under mild conditions without the use of transition metals, affording the target products in moderate to good yields, and this cyclization reaction process can be scaled up to a gram-scale synthesis.
- Wei, Hao-Zhao,Li, Quan-Zhe,Wei, Yin,Shi, Min
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p. 7396 - 7400
(2020/10/13)
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- Experimental and Computational Studies on Cp*CyRh(III)/KOPiv-Catalyzed Intramolecular Dehydrogenative Cross-Couplings for Building Eight-Membered Sultam/Lactam Frameworks
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Described herein is an unusual Cp*CyRh(III)-catalyzed intramolecular site-specific aryl C-H annulation, a highly chemoselective protocol providing direct access to eight-membered sultams/lactams with broad substrate/functional group tolerance. Experimental and computational studies reveal that such a transformation involves a unique PivOH-assisted aryl C-H activation/alkene insertion/β-H elimination/hydrogen-transfer process involving the Rh(III)-hydride species as the active intermediate with the concomitant release of H2 as the major byproduct, thus enabling the developed Cp*CyRh(III) catalysis with redox-neutral and highly atom-economical features.
- Li, Liping,Gao, Hui,Sun, Ming,Zhou, Zhi,Yi, Wei
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p. 5473 - 5478
(2020/07/14)
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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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- 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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- Xantphos-ligated palladium dithiolates: An unprecedented and convenient catalyst for the carbonylative Suzuki–Miyaura cross-coupling reaction with high turnover number and turnover frequency
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Xantphos- and dithiolate-ligated macrocyclic palladium complexes as an efficient and stable catalyst for the carbonylative Suzuki–Miyaura cross-coupling reaction have been synthesized. The catalysts were characterized by 1H-nuclear magnetic resonance (NMR), CHNS (carbon, hydrogen, nitrogen, and sulfur) analysis, melting point analysis, and 31P-NMR spectroscopy. Several sensitive functional groups (e.g., –NO2, –F, –Cl, –Br, –NH2, and –CN) on the aromatic ring were well tolerated in the carbonylative Suzuki–Miyaura coupling reaction. The present palladium complexes produce six times higher turnover number (TON) and five times higher turnover frequency (TOF) compared with conventional homogeneous palladium precursors. Maximum TONs in the range of 105 to 106 and TOF in the range of 104 to 105 could be generated by a very low amount of catalyst loading (10–5?mol%).
- Gaikwad, Vinayak V.,Mane, Pravin A.,Dey, Sandip,Bhanage, Bhalchandra M.
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- Quinazoline fluorescent probe and preparation method and application thereof
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The invention belongs to the technical field of biomedicine and particularly relates to a quinazoline fluorescent probe and a preparation method and application thereof. The chemical formula of the quinazoline fluorescent probe is shown in the formula I, wherein R is selected from H or Cl; R is selected from fluorescent molecules; and n is an integer from 2 to 8. Through the quinazoline fluorescent probe and the preparation method and application thereof, the interference of autofluorescence of an organism can be eliminated, and the TSPO content in the organism can be detected efficiently and accurately.
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Paragraph 0049; 0058-0060
(2020/02/27)
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- Novel Biomass-Derived Fe3O4@Pd NPs as Efficient and Sustainable Nanocatalyst for Nitroarene Reduction in Aqueous Media
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Abstract: A novel magnetically recyclable nitrogen-doped Fe3O4@Pd NPs was prepared from the biomass-based materials which was employed as carbon and nitrogen source. The as-prepared catalysts were fully characterized by a variety of physicochemical techniques and were exploited for nitroaromatic hydrogenation with broad scope and excellent chemoselectivity using molecular hydrogen as a reductant. The heterogeneous catalysts can be recovered easily and reused for at least eight recycling reactions without obviously loss of catalytic properties. In addition, using this protocol, the key intermediate of marketed drug Osimertinib could be synthesized easily. Graphical Abstract: [Figure not available: see fulltext.].
- Zhao, Linwei,Zheng, Kai,Tong, Jianying,Jin, Jianzhong,Shen, Chao
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p. 2607 - 2613
(2019/06/08)
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- Palladium-Catalyzed Late-Stage ortho-C-H Bond Aroylation of Anilines Using 4-Methoxy-2-pyridinyl as a Removable Directing Group
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A synthetic methodology for the late-stage ortho-C-H bond aroylation of anilines with aryl aldehydes led to a variety of ortho-aroylated anilines by the use of palladium(II) acetate, tert-butyl hydroperoxide, and 1,4-dioxane as the catalyst, oxidant, and solvent, respectively, is presented. An N-phenylpyridin-2-amine palladacycle was isolated and characterized by X-ray crystallography. Controlled experiments, radical trapping experiments, and the experiments of the kinetic isotope effect were undertaken to support the proposed reaction mechanism. Syntheses of 2-aminobenzophenone and 9(10H)-acridanone based on the developed methodology were successfully demonstrated.
- Chu, Jean-Ho,Chiang, Meng-Fan,Li, Chin-Wei,Su, Zhe-Hong,Lo, Shao-Chi,Wu, Ming-Jung
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p. 2105 - 2119
(2019/05/08)
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- Synthesis of Diiodinated All-Carbon 3,3′-Diphenyl-1,1′-spirobiindene Derivatives via Cascade Enyne Cyclization and Electrophilic Aromatic Substitution
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A synthetic method for the construction of diiodinated all-carbon spirobiindene derivatives has been developed from the reaction of propargyl alcohol-tethered alkylidenecyclopropanes with iodine. The reaction proceeded through an iodination-initiated cascade intramolecular enyne cyclization and electrophilic aromatic substitution reaction process in 1,2-dichloroethane upon heating, giving desired spirocyclic products in moderate to excellent yields. Further transformation of the obtained products has also been presented.
- Li, Quanzhe,Yu, Liuzhu,Wei, Yin,Shi, Min
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p. 9282 - 9296
(2019/08/12)
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- Deoxygenative Arylation of Carboxylic Acids by Aryl Migration
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An unprecedented deoxygenative arylation of aromatic carboxylic acids has been achieved, allowing the construction of an enhanced library of unsymmetrical diaryl ketones. The synergistic photoredox catalysis and phosphoranyl radical chemistry allows for precise cleavage of a stronger C?O bond and formation of a weaker C?C bond by 1,5-aryl migration under mild reaction conditions. This new protocol is independent of substrate redox-potential, electronic, and substituent effects. It affords a general and promising access to 60 examples of synthetically versatile o-amino and o-hydroxy diaryl ketones under redox-neutral conditions. Furthermore, it also brings one concise route to the total synthesis of quinolone alkaloid, (±)-yaequinolone A2, and a viridicatin derivative in satisfying yields.
- Ruzi, Rehanguli,Ma, Junyang,Yuan, Xiang-Ai,Wang, Wenliang,Wang, Shanshan,Zhang, Muliang,Dai, Jie,Xie, Jin,Zhu, Chengjian
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p. 12724 - 12729
(2019/11/05)
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- Palladium-Catalyzed Cascade Reductive and Carbonylative Cyclization of Ortho-Iodo-Tethered Methylenecyclopropanes (MCPs) Using N-Formylsaccharin as CO Source
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A palladium-catalyzed reductive and carbonylative cyclization of ortho-iodo-tethered methylenecyclopropanes (MCPs) using N-formylsaccharin as CO source has been developed, affording the desired indanone derivatives in moderate to good yields with high regio- and stereoselectivity and good functional group compatibility.
- Fan, Xing,Shi, Min,Wei, Yin
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p. 5677 - 5683
(2019/11/16)
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- Lewis or Br?nsted acid-catalysed reaction of propargylic alcohol-tethered alkylidenecyclopropanes with indoles and pyrroles for the preparation of polycyclic compounds tethered with indole or pyrrole motif
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We developed a facile synthetic method to access cyclopenta[b]naphthalene derivatives via the Lewis or Br?nsted acid catalysed cascade nucleophilic addition, electronic cyclization, ring-opening rearrangement of propargylic alcohol-tethered alkylidenecyclopropanes with indole and pyrrole derivatives. The reaction exhibited a broad substrate scope and good functional group tolerance under metal-free conditions, affording the desired products in moderate to good yields.
- Wei, Hao-Zhao,Yu, Liu-Zhu,Shi, Min
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p. 135 - 139
(2019/12/26)
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- Design, synthesis, crystal structures, and photophysical properties of tetraphenylethene-based quinoline derivatives
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The incorporation of aggregation-induced emission (AIE) luminogens provides a molecule with enhanced fluorescent emission in the solid state. A representative AIEgen compound is tetraphenylethene (TPE). A series of new conjugates of quinolone derivatives with TPE units (1a - 1f) was synthesized and characterized. The influence on the photophysics of 1a - 1e with a variety of functional groups was investigated systematically by spectroscopic methods and simulated by density-functional theory calculations. A centrosymmetric compound donor-acceptor-donor-type compound 1f with two TPE moieties proved to be the most promising multifunctional material, it exhibited tri-colored (489–569 nm) fluorescence characteristics in tetrahydrofuran-H2O solution with a different water fraction and intense tri-colored solvatochromic (blue, green, and yellow) behaviors. These compounds could be applied as promising acid-base gas probe based on their evident color switch. Compounds 1a - 1f showed the advantage of being a potential piezochromic material.
- Zhu, Xiaolin,Wang, Danfeng,Huang, Hai,Zhang, Xueqiong,Wang, Shifan,Liu, Rui,Zhu, Hongjun
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- Method for synthesizing ortho-amino aromatic ketone from aromatic carboxylic acid
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Disclosed is a method for synthesizing ortho-amino aromatic ketone from aromatic carboxylic acid. The method comprises the steps that with 2-arylsulfonamido aromatic carboxylic acid shown in the description as a raw material and triphenylphosphine as a deoxidizer, under the illumination of blue light, in a 1,4-dioxane solution, under an argon atmosphere, in the presence of the dipotassium hydrogenphosphate, with [Ir(dF(CF3)ppy)2(dtbbpy)]PF6 as a photocatalyst, the ortho-amino aromatic ketone compound is obtained; the structure of the photocatalyst [Ir(dF(CF3)ppy)2(dtbbpy)]PF6 is shown in thedescription.
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Paragraph 0023; 0024
(2019/07/04)
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- The Reaction of o-Aminoacetophenone N-Tosylhydrazone and CO2 toward 1,4-Dihydro-2H-3,1-benzoxazin-2-ones
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A transition-metal-free reaction of o-aminoacetophenone N-tosylhydrazone and CO2 has been developed, leading to a series of 1,4-dihydro-2H-3,1-benzoxazin-2-ones in moderate to good yields. This procedure proceeds with the sequential fixation of CO2 by amino leading to carbamic acid and the intra- molecular insertion of hydroxyl to carbene. (Figure presented.).
- Xiong, Hao,Wu, Xiaopeng,Wang, Hepan,Sun, Song,Yu, Jin-Tao,Cheng, Jiang
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supporting information
p. 3538 - 3542
(2019/07/10)
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- Polymer-incarcerated palladium-catalyzed facile: In situ carbonylation for the synthesis of aryl aldehydes and diaryl ketones using CO surrogates under ambient conditions
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In this existing work, an efficient polymer-supported palladium catalyst, a furfurylamine-functionalized Merrifield complex of palladium [Pd@(Merf-FA)], was synthesized and characterized, showing excellent catalytic activity towards in situ carbonylation reactions using carbon monoxide surrogates like formic acid and chloroform. Herein, we examined the catalytic activity of the Pd@(Merf-FA) catalyst for the formylation of aryl iodides and carbonylative Suzuki-Miyaura coupling reactions. The Pd@(Merf-FA) catalyst was systematically characterized by several techniques like HRTEM, elemental mapping, PXRD, TGA-DTA, FESEM, UV-vis, EDAX, CHN and AAS analysis. The catalyst is highly recyclable, able to be recycled up to six times without showing any significant decrease in catalytic activity. The [Pd@(Merf-FA)] catalyst proved to be more efficient compared to the corresponding homogeneous palladium catalyst. In addition, the leaching experiment of the synthesized catalyst was studied, which showed that negligible leaching of metal occurred from the polymeric support.
- Dey, Tusar Kanto,Basu, Priyanka,Riyajuddin, Sk,Ghosh, Aniruddha,Ghosh, Kaushik,Manirul Islam, Sk
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p. 9802 - 9814
(2019/07/04)
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- Gold-catalyzed cyclization of 1-(2′-Azidoaryl) propynols: Synthesis of polysubstituted 4-quinolones
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An unprecedented gold-catalyzed procedure for the synthesis of polysubstituted 4-quinolones from 1-(2′-Azidoaryl) propynols is described. The reaction undergoes an intramolecular nucleophilic attack of the azide group to the Au-Activated triple bonds in a 6-endo-dig manner and subsequent gold-Assisted expulsion of N2 to furnish an α-imino gold carbene intermediate, which triggers a 1,2-carbon migration and finally is converted to 2,3-disubstituted 4-quinolone.
- Wu, Xiang,Zheng, Lang-Lang,Zhao, Li-Ping,Zhu, Cheng-Feng,Li, You-Gui
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supporting information
p. 14769 - 14772
(2019/12/24)
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- Iron-Promoted Construction of Indoles via Intramolecular Oxidative C-N Coupling of 2-Alkenylanilines Using Persulfate
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Indole scaffold synthesis relies primarily on oxidative C-H amination of N-protected alkenylanilines for C-N intramolecular cyclization reactions. Herein, for the first time, without N-protection, various readily prepared 2-alkenylanilines were transformed into the desired indole products in good yields by using K 2 S 2 O 8 as oxidant in the presence of catalytic amounts of FeF 2. The K 2 S 2 O 8 /FeF 2 system offers a direct and benign synthetic route to 3-arylindoles and it is applicable to a wide range of substituted indoles including drug intermediates.
- Li, Yudong,Li, Yuehui,Luo, Shuping,Wang, Menglan,Wu, Qing-An
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supporting information
p. 3085 - 3090
(2019/08/07)
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- Chemo-selective reduction of nitro and nitrile compounds using Ni nanoparticles immobilized on hyperbranched polymer-functionalized magnetic nanoparticles
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The nitro and nitrile groups in aromatic and aliphatic compounds containing various reducible substituents such as carboxylic acid, ketone, aldehyde and halogen are selectively reduced to the corresponding amines in water as a green solvent with excellent yields by employing NaBH4 in the presence of Fe3O4@PAMAM/Ni(0)-b-PEG nanocatalyst. The morphology and structural features of the catalyst were characterized using various microscopic and spectroscopic techniques. The designed catalyst system because of it being covered with hydrophilic polymers is soluble in a wide range of solvents (e.g. water and ethanol) and suitable for immobilizing and stabilizing Ni nanoparticles in aqueous mediums. In addition, the catalyst can be easily recovered from a reaction mixture by applying an external magnetic field and can be reused up to six runs without significant loss of activity.
- Tabatabaei Rezaei, Seyed Jamal,Mashhadi Malekzadeh, Asemeh,Poulaei, Sima,Ramazani, Ali,Khorramabadi, Hossein
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- Bioactive 3,4,5-substituted benzodiazepine 2-one drug molecules and preparation method thereof
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The invention discloses bioactive 3,4,5-substituted benzodiazepine 2-one drug molecules and a preparation method thereof and belongs to the technical field of drug synthesis. The technical scheme is characterized in that the structure of the compounds is shown in the description, wherein R1 is methyl, pyridyl, phenyl or isopropyl; R1 and R2 are selected from methyl, ethyl or phenyl independently respectively. Compared with the prior art, the compounds and the preparation method have the following beneficial effects: the synthesis method is simple, the molecular structure is novel, and the compounds have an inhibition effect on the leukemia cell line K562 and the breast cancer cell MCF-7 and are expected to be further popularized and applied.
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- Catalyst-free geminal aminofluorination of ortho-sulfonamide-tethered alkylidenecyclopropanes via a Wagner-Meerwein rearrangement
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A catalyst-free intramolecular geminal aminofluorination of ortho-sulfonamide-tethered alkylidenecyclopropanes has been developed. The reaction proceeded through two SET processes with Selectfluor to give a fluorinated cyclopropylcarbinyl cation and a further Wagner-Meerwein rearrangement to generate a cyclobutyl carbocation, which undergoes intramolecular nucleophilic capture by amide to forge fluorinated cyclobuta[b]indoline derivatives. A polycyclic multi-fluorinated byproduct was also formed through a Ritter-type reaction in some cases.
- Fan, Xing,Wang, Qiang,Wei, Yin,Shi, Min
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p. 10503 - 10506
(2018/09/21)
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- Palladium Catalyzed Direct Acylation of Iodo-Acetanilides/Iodo-Phenyl Acetates: Domino One-Pot Synthesis of 2-Quinolinones
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Pd-catalyzed direct acylation reaction of iodoacetanilides/iodophenyl acetates with aldehydes is presented. Simple, bench-top aldehydes were used as non-toxic acylating agents. This protocol comprises direct coupling with aldehydes without activating the carbonyl group and without directing group assistance. The strategy was applied to a domino one-pot synthesis of 2-quinolinones through acylation and intramolecular aldol condensation. Significantly, the strategy was extended to the domino one-pot synthesis of drugs and bioactive compounds.
- Basuli, Scuhand,Satyanarayana, Gedu
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p. 957 - 970
(2017/12/07)
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- Water-Soluble Hypervalent Iodine(III) Having an I-N Bond. A Reagent for the Synthesis of Indoles
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A readily accessible and bench-stable water-soluble hypervalent iodine(III) reagent (phenyliodonio)sulfamate (PISA) with an I-N bond was synthesized, and its structure was characterized by X-ray crystallography. With PISA, various indoles were synthesized via C-H amination of 2-alkenylanilines involving an aryl migration/intramolecular cyclization cascade with excellent regioselectivity in aqueous CH3CN. Notably, using this new method as the key step, not only two drug molecules, indometacin and zidometacin, but also another bioactive molecule, pravadoline, were synthesized.
- Xia, Hai-Dong,Zhang, Yan-Dong,Wang, Yan-Hui,Zhang, Chi
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supporting information
p. 4052 - 4056
(2018/07/15)
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- Copper-Catalyzed Synthesis of Substituted Quinazolines from Benzonitriles and 2-Ethynylanilines via Carbon-Carbon Bond Cleavage Using Molecular Oxygen
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A copper-catalyzed process for the synthesis of substituted quinazolines from benzonitriles and 2-ethynylanilines using molecular oxygen (O2) as sole oxidant is described. The mild catalytic system enabled the effective cleavage of the C-C triple bond and construction of new C-N and C-C bonds in one operation. Furthermore, the compound N,N-dimethyl-4-(2-(4-(trifluoromethyl)phenyl)quinazolin-4-yl)aniline (3dj) exhibited obvious aggregation-induced emission phenomenon, and the fluorescence quantum yield (ΦF,film) and lifetime (τfilm) were measured to be 45.5% and 5.8 ns in thin films state, respectively.
- Wang, Xu,He, Dandan,Huang, Yubing,Fan, Qihang,Wu, Wanqing,Jiang, Huanfeng
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p. 5458 - 5466
(2018/05/28)
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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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- Cu(I)-Catalyzed Coupling and Cycloisomerization of Diazo Compounds with Terminal Yne-Alkylidenecyclopropanes: Synthesis of Functionalized Cyclopenta[ b]naphthalene Derivatives
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A Cu(I)-catalyzed coupling and cycloisomerization of diazo compounds with terminal yne-alkylidenecyclopropanes (ACPs) has been presented. This reaction starts from the formation of an allenic intermediate in the Cu(I)-catalyzed cross-coupling reaction of a diazo compound with terminal alkyne in yne-tethered ACP and then undergoes a domino cycloisomerization of a 6π-electrocyclization and cyclopropane ring-opening rearrangement to give functionalized cyclopenta[b]naphthalene derivatives in moderate to excellent yields under mild conditions.
- Li, Peng-Hua,Yu, Liu-Zhu,Zhang, Xiao-Yu,Shi, Min
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p. 4516 - 4520
(2018/08/09)
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- Palladium-Catalyzed Three-Component Tandem Process: One-Pot Assembly of Quinazolines
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The first example of the palladium-catalyzed, three-component tandem reaction of 2-aminobenzonitriles, aldehydes, and arylboronic acids has been developed, providing a new approach for one-pot assembly of diverse quinazolines in moderate to good yields. A noteworthy feature of this method is the tolerance of bromo and iodo groups, which affords versatility for further synthetic manipulations. Preliminary mechanistic experiments indicate that this tandem process involves two possible mechanistic pathways for the formation of quinazolines via catalytic carbopalladation of the cyano group.
- Hu, Kun,Zhen, Qianqian,Gong, Julin,Cheng, Tianxing,Qi, Linjun,Shao, Yinlin,Chen, Jiuxi
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supporting information
p. 3083 - 3087
(2018/05/28)
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- Electrophilic activation of aminocarboxylic acid by phosphate ester promotes Friedel-Crafts acylation by overcoming charge-charge repulsion
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Friedel-Crafts acylation of aromatic compounds with aminocarboxylic acids proceeds efficiently in the presence of a tailored phosphate ester and a strong Br?nsted acid, despite the strong charge-charge repulsion associated with acylium ion formation. Here, we investigate the mechanism of this electrophilic aromatic acylation reaction, focusing on how the aminocarboxylic acid is activated by the phosphate ester and how the charge-charge repulsion is overcome. In the first step of the reaction, an acyl phosphate is generated from the aminocarboxylic acid through the intervention of the phosphate ester, which possesses three methyl salicylate ester linkages. The o-methyl salicylates enhance the reactivity of the phosphate ester via a protonation-induced conformational change, thereby overwhelming the charge-charge repulsion associated with the acylium ion formation. Weakening of the resonance interaction in the C(O)-O(P) bond by the lone-pair electrons of the ether oxygen atom of the carboxylic acid functionality contributes to the rapid formation of the acylium ion. Thus, our results show that the formation of aromatic ketones from various carboxylic acids proceeds because the strong leaving ability of the acyl phosphate overwhelms the charge-charge repulsion associated with the formation of the acylium ion. This information will be helpful to improve the design of tailored phosphate reagents.
- Sumita, Akinari,Otani, Yuko,Ohwada, Tomohiko
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p. 9398 - 9407
(2017/11/22)
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- Synthetic method of 2-chloro-4-phenyl quinazoline
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The invention relates to a synthetic method of 2-chloro-4-phenyl quinazoline and belongs to the technical field of organic synthetic chemistry. The synthetic method comprises the following steps of: by taking o-benzoylbenzoic acid as a raw material, performing an acylating chlorination reaction to generate o-benzoyl benzoyl chloride; performing an amidation reaction to generate o-benzoyl benzamide; performing a Hofmann degradation reaction to generate 2-amino benzophenone; and performing an annulations reaction to generate 4-phenyl quinazoline-2(1H)-one and chlorinating the 4-phenyl quinazoline-2(1H)-one by phosphorus oxychloride to finally generate 2-chloro-4-phenyl quinazoline, wherein the total yield is 20.8%. Compared with other methods, the reagents used by the route are low in price and easily available, and the post-treatment is simple. In the reaction process, the reaction conditions and synthetic processes thereof are explored, so that a simple and feasible synthetic route is provided for synthesizing 2-chloro-4-phenyl quinazoline, thereby realizing amplified production.
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Paragraph 0019; 0020
(2017/09/01)
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- Oxidative Fragmentations and Skeletal Rearrangements of Oxindole Derivatives
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An oxidative sequence for the conversion of oxindoles to structurally distinct heterocyclic scaffolds and aniline derivatives is disclosed by the combination of a copper-catalyzed C-H peroxidation and subsequent base-mediated fragmentation reaction. In contrast to classic enzymatic (i.e., kynurenine pathway) and biomimetic methods (i.e., Witkop-Winterfeldt oxidation) for oxidative indole cleavage, this protocol allows for the incorporation of external nucleophiles. The new transformation displays broad functional group tolerance and is applicable to tryptophan derivatives, opening potential new avenues for postsynthetic modification of polypeptides, bioconjugation, and unnatural amino acid synthesis.
- Klare, Hendrik F. T.,Goldberg, Alexander F. G.,Duquette, Douglas C.,Stoltz, Brian M.
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supporting information
p. 988 - 991
(2017/03/14)
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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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- Cascade Amination/Cyclization/Aromatization Process for the Rapid Construction of [2,3-c]Dihydrocarbazoles and [2,3-c]Carbazoles
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An intramolecular cascade amination/cyclization/aromatization reaction of functionalized alkylidenecyclopropanes has been developed in the presence of silver acetate, affording a variety of [2,3-c]dihydrocarbazoles and [2,3-c]carbazoles in moderate to excellent yields. The mechanistic investigations revealed that this cascade reaction proceeds through a radical initiated process. Moreover, further transformations for the synthesis of eustifoline-D and an OLED exhibit a potential synthetic utility of this method.
- Fan, Xing,Yu, Liu-Zhu,Wei, Yin,Shi, Min
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p. 4476 - 4479
(2017/09/11)
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- Chemoselective generation of acyl phosphates, acylium ion equivalents, from carboxylic acids and an organophosphate ester in the presence of a Br?nsted acid
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We describe the chemoselective conversion of carboxylic acids to functional aromatic ketones promoted by a tailored organophosphate ester in the presence of a Br?nsted acid. The protonated phosphate ester reacts with the carboxylic acid to form acyl phosphate, which reacts with benzenes to give aromatic ketones, probably through the acylium ion or its equivalent. The reaction time is short even at room temperature, and the reaction is compatible with various other functional groups, including amines, olefins, esters, amides and nitriles.
- Sumita, Akinari,Otani, Yuko,Ohwada, Tomohiko
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supporting information
p. 1482 - 1485
(2017/02/05)
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- Efficient Friedel–Crafts benzoylation of aniline derivatives with 4-fluorobenzoyl chloride using copper triflate in the synthesis of aminobenzophenones
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ABSTRACT: An efficient pathway for the synthesis of the aminobenzophenone derivatives via Friedel–Crafts benzoylation using copper triflate as catalyst is proposed. New derivatives are synthesized. The copper triflate could be easily recovered and reused without loss of catalytic activity. Both the use of ionic liquids and microwave heating turned out to be fruitful.
- Tran, Phuong Hoang,Phung, Huy Quang,Hansen, Poul Erik,Tran, Hai Ngoc,Le, Thach Ngoc
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p. 893 - 901
(2016/07/06)
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- Intramolecular addition of diarylmethanols to imines promoted by KO: T -Bu/DMF: A new synthetic approach to indole derivatives
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KOt-Bu/DMF promoted intramolecular addition of diarylmethanols to imines was developed. A series of 2,3-disubstituted indoles was obtained in good yields. A reaction mechanism of radical cyclization and subsequent dehydration is proposed.
- Chen, Jia-Hua,Chen, Zi-Cong,Zhao, Hong,Zhang, Ting,Wang, Wei-Juan,Zou, Yong,Zhang, Xue-Jing,Yan, Ming
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supporting information
p. 4071 - 4076
(2016/06/14)
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- Carbonylative coupling of aryl tosylates/triflates with arylboronic acids under CO atmosphere
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The carbonylative Suzuki-Miyaura reaction between aryl tosylates/triflates with arylboronic acid is herein reported, using base-free conditions and a balloon pressure of carbon monoxide. Under these conditions, unsymmetrical biaryl ketones were obtained in modest to excellent yields. This method was adapted to the synthesis of oxybenzone and ketoprofen in good yields under mild conditions.
- Hao, Cheng Yi,Wang, Dan,Li, Ya Wei,Dong, Lin Lin,Jin, Ying,Zhang, Xiu Rong,Zhu, He Yun,Chang, Sheng
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p. 86502 - 86509
(2016/09/23)
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- Reactivity of 2,1-Benzisoxazole in Palladium-Catalyzed Direct Arylation with Aryl Bromides
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The Pd-catalyzed direct arylation of 2,1-benzisoxazole with aryl bromides to access 3-arylbenzoisoxazoles proceeds in moderate-to-high yields with 1 mol % Pd(OAc)2 or 2 mol % PdCl(C3H5)(dppb) (dppb=1,4-bis(diphenylphosphino)butane) as the catalysts and KOAc as an inexpensive base. A wide variety of (hetero)aryl bromides have been employed successfully. Moreover, arylations followed by benzisoxazole ring opening allowed the preparation of 2-aminobenzophenones in only two steps. What a couple: The Pd-catalyzed direct arylation of 2,1-benzisoxazole with aryl bromides and 1 mol % of phosphine-free Pd(OAc)2 catalyst in association with KOAc as an inexpensive base allows the preparation of 3-arylbenzoisoxazoles in moderate-to-high yields. Moreover, the 2,1-benzisoxazole C-3-arylations followed by benzisoxazole ring opening gives access to 2-aminobenzophenones in only two steps.
- Aidene, Mohand,Belkessam, Fatma,Soulé, Jean-Fran?ois,Doucet, Henri
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p. 1583 - 1590
(2016/05/02)
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- Photo-catalytic selectivity of anthranilic acid over iron oxide incorporated titania nanoparticles: Influence of the Fe2+/Fe3+ ratio of iron oxide
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Iron oxide incorporated titania nanoparticles (FIT) with various atomic ratios of Fe/Ti, i.e. 3.53% (FIT-1), 8.3% (FIT-2), and 20.79% (FIT-3), are prepared to monitor the selectivity of photo-degradation for anthranilic acid (AA) in molecular level. In the FIT-1 route, the products obtained from the photo-degradation of AA are aniline, 4-aminophenol, and benzene. Since the surface of iron oxide domain in FIT-1 is fully reduced to FeO. The FeO, by trapping the photo-generated (e-), acts as a Lewis base to facilitate the de-carboxylation reaction for AA to create aniline. It is noteworthy that the highly alkaline surface of FIT-1 executes the hydroxylation addition for AA to produce 4-aminophenol. In FIT-2, and FIT-3 routes, the surface of incorporated iron oxide is only partially reduced to FeO. After the photo-degradation of AA, the collected products are 2-aminobenzaldehyde, and benzene. In this route, the low spin (LS) Fe3+ ion in the Fe2O3 region adopts the photo-generated (e-). The LS Fe3+ is reduced to stable LS Fe2+, i.e. FeO. At this stage, the Fe2O3 domain acts as a Lewis acid to push forward the carbonyl reduction of AA to obtain 2-aminobenzaldehyde. In addition, the de-amination is contributed by the nucleorphilic attack of water molecule to the carbon atom of aromatic ring bonded to NH2 group. After the de-amination reaction, the intermediate product is phenol. The following de-hydroxyl reaction by FeO domain proceeds immediately. The final product is benzene that is observed in all FIT involved catalytic routes.
- Chang, Ya-Hui,Ou, Chun-Chang,Yeh, Hui-Wen,Yang, Chung-Sung
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- Bi (NO3)3·5H2O and cellulose mediated Cu-NPs - A highly efficient and novel catalytic system for aerobic oxidation of alcohols to carbonyls and synthesis of DFF from HMF
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A highly efficient and versatile catalytic system for oxidation of primary and secondary aromatic alcohols to carbonyls has been developed. High efficiency, general synthetic applicability, broader functional group tolerance and versatility towards oxidation of both primary and secondary aromatic alcohols are the key features of this green and sustainable protocol. Selective oxidation of 5-hydroxymethyl furfural (HMF) to biofuel 2,5-diformylfuran (DFF) has been observed in excellent yields. Use of sustainable bio-polymer cellulose as a Cu-nanoparticle support makes the catalytic system environmentally benign.
- Baruah, Diganta,Hussain, Farhaz L.,Suri, Mrinaly,Saikia, Ujwal Pratim,Sengupta, Pinaki,Dutta, Dipak Kumar,Konwar, Dilip
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- KCC-1 supported palladium nanoparticles as an efficient and sustainable nanocatalyst for carbonylative Suzuki-Miyaura cross-coupling
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This work reports a cost-effective and sustainable protocol for the carbonylative Suzuki-Miyaura cross-coupling reaction catalyzed by palladium nanoparticles (Pd NPs) supported on fibrous nanosilica (KCC-1). Under mild reaction conditions, the KCC-1-PEI/Pd catalytic system showed a turnover number (TON) 28-times and a turnover frequency (TOF) 51-times higher than the best supported Pd catalyst reported in the literature for the carbonylative cross-coupling between 4-iodoanisole and phenylboronic acid, as a test reaction. Also, the catalyst could be recycled up to ten times with a marginal loss in activity after the eighth cycle. The high activity of the catalyst can be attributed to the fibrous nature of the KCC-1 support and PEI functionalization provided the enhanced stability.
- Gautam, Prashant,Dhiman, Mahak,Polshettiwar, Vivek,Bhanage, Bhalchandra M.
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supporting information
p. 5890 - 5899
(2016/11/06)
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- 2-Arylindoles: A new entry to transition metal-free synthesis of 2-aminobenzophenones
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Various 2-aminobenzophenones were synthesized from readily available 2-arylindoles in DMSO under O2 balloon atmosphere. The synthesis was carried out without the aid of a transition metal catalyst or moisture-sensitive organometallic reagents from 2-arylindoles.
- Yu, Jin,Moon, Hye Ran,Min, Beom Kyu,Kim, Jae Nyoung
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p. 893 - 897
(2016/06/14)
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- Palladium nanoparticles immobilized onto supported ionic liquid-like phases (SILLPs) for the carbonylative Suzuki coupling reaction
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Crosslinked polymeric materials based on poly(ionic liquid)s, also named supported ionic liquid-like phases (SILLPs) were prepared by copolymerization of dication imidazole ionic liquids with divinylbenzene (DVB). Using the SILLPs-related polymeric materials as supports, palladium (Pd) metal nanoparticles were immobilized and stabilized, which can efficiently catalyze the carbonylative Suzuki coupling reaction of aryl iodides with aryl boronic acids, affording the corresponding products in good to excellent yields. The Pd nanoparticles immobilized onto SILLPs were characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TG), and X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR). The size and dispersion of the Pd nanoparticles supported on polymers are influenced possibly by varying the contents of the ionic liquid units and the introduction of amine groups. Furthermore, hot filtration and mercury poisoning tests indicated that the palladium species leached into the solvent during the reaction and returned to the polymers after the reaction was completed. In addition, the catalyst was easily recovered from the reaction mixture by filtration and reused over five consecutive cycles without a significant decrease in its activity. This journal is
- Jiao, Nianming,Li, Zelong,Wang, Yan,Liu, Jianhua,Xia, Chungu
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p. 26913 - 26922
(2015/03/30)
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- Divergent Reactivity of Rhodium(I) Carbenes Derived from Indole Annulations
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Rhodium(I) carbenes were generated from propargylic alcohol derivatives as the result of a dehydrative indole annulation. Depending on the choice of the electron-withdrawing group on the aniline nitrogen nucleophile, either a cyclopropanation product or dimerization product was obtained chemoselectively. Intramolecular hydroamidation occurred for the same type of propargylic alcohol derivatives when other transition-metal catalysts were employed.
- Li, Xiaoxun,Li, Hui,Song, Wangze,Tseng, Po-Sen,Liu, Lingyan,Guzei, Ilia A.,Tang, Weiping
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supporting information
p. 12905 - 12908
(2015/11/02)
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- Palladacycle-Catalyzed Carbonylative Suzuki-Miyaura Coupling with High Turnover Number and Turnover Frequency
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This work reports the carbonylative Suzuki-Miyaura coupling of aryl iodides catalyzed by palladacycles. More importantly, the palladacycles have been used to generate high turnover numbers (TON's) and turnover frequencies (TOF's). A range of aryl iodides can be coupled with arylboronic acids, generating TON's in the range of 106 to 107 and TOF's in the range of 105 to 106 h-1. Comparison of the palladacycles with a conventional palladium source shows their superiority in generating high TON's and TOF's.
- Gautam, Prashant,Bhanage, Bhalchandra M.
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p. 7810 - 7815
(2015/08/18)
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