- Synthesis of symmetric anhydrides using visible light-mediated photoredox catalysis
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A new approach to anhydride formation is reported via activation of C-O bonds by the Vilsmeier-Haack reagent formed by Ru(bpy)3Cl2 and CBr4 in DMF. Various aryl and alkyl carboxylic acids are converted to the corresponding anhydrides in excellent yields.
- Konieczynska, Marlena D.,Dai, Chunhui,Stephenson, Corey R. J.
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- Cu-MOF: An efficient heterogeneous catalyst for the synthesis of symmetric anhydrides: Via the C-H bond activation of aldehydes
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In this paper, an efficient and straightforward synthetic approach for the preparation of a number of symmetric carboxylic anhydrides was reported using Cu2(BDC)2(DABCO) as an efficient heterogeneous catalyst via the C-H bond activation of aldehydes with excellent yields and simple work up. This C-H bond activation reaction appears simple and convenient, has a wide substrate scope and makes use of cheap, abundant, and easily available reagents. The Cu-MOF catalyst was recycled and reused four times without any loss of catalytic activity.
- Ahmadzadeh, Zahra,Mokhtari, Javad,Rouhani, Morteza
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- Synthesis of anhydrides from acyl chlorides under ultrasound condition
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A convenient and general method for the synthesis of symmetrical anhydrides under ultrasound conditions is described.
- Hu, Yulai,Wang, Jin-Xian,Li, Shihua
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- Synthesis, molecular docking, and pharmacological evaluation of N-(2-(3,5-dimethoxyphenyl)benzoxazole-5-yl)benzamide derivatives as selective COX-2 inhibitors and anti-inflammatory agents
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A series of N-(2-(3,5-dimethoxyphenyl)benzoxazole-5-yl)benzamide derivatives (3am) was synthesized and evaluated for their in vitro inhibitory activity against COX-1 and COX-2. The compounds with considerable in vitro activity (IC50 50 values in the range of 0.06–0.71 μM. The in vivo anti-inflammatory activity of these six compounds (3a, 3b, 3d, 3g, 3j, and 3k) was assessed by the carrageenan-induced rat paw edema method. Compounds 3d (84.09%), 3g (79.54%), and 3a (70.45%) demonstrated significant anti-inflammatory activity compared to the standard drug ibuprofen (65.90%) and were also found to be safer than ibuprofen, by ulcerogenic studies. A docking study was done using the crystal structure of human COX-2, to understand the binding mechanism of these inhibitors to the active site of COX-2.
- Kaur, Avneet,Pathak, Dharam P.,Sharma, Vidushi,Wakode, Sharad
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- FACILE CONVERSION OF AMIDES TO THE ACIDS AND/OR ANHYDRIDES USING DINITROGEN TETROXIDE
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Carboxamides and sulfonamides were reacted with dinitrogen tetroxide to give the corresponding acids, while such as N-bromoamides and hydroxamic acids were also converted to the corresponding acids together with their anhydrides.
- Kim, Yong Hae,Kim, Kweon,Park, Young Jun
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- Efficient Preparation of 2-Deoxy-3,5-di-O-p-toluoyl-α-D- ribofuranosyl Chloride
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An efficient method for the synthesis of 1-O-methyl-3,5-di-O-p-toluoyl-2- deoxy-α/β-D-ribose is described. Upon treatment with HCl, 2-deoxy-3,5-di-O-p-toluoyl-α-D-ribofuranosyl chloride, previously unstable, was produced as a white solid, stable in air indefinitely.
- Dhimitruka, Ilirian,SantaLucia Jr., John
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- OXYGEN ATOM TRANSFER REACTION. THE REACTION OF CARBONYL COMPOUNDS WITH DIOXYGEN COMPLEXES
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The reaction of peroxobis(triphenylphosphine)platinum with benzil or benzoic anhydride gave benzoic anhydride or benzoyl peroxide respectively.The scope of the above reactions is described.
- Aida, Shun'ichi,Ohta, Hiroyuki,Kamiya, Yoshio
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- Efficient synthesis of symmetrical anhydrides by cross dehydrogenative coupling of aryl aldehydes over CuFe2O4 nanoparticles
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Nano copper ferrite catalyst is prepared and characterized by scanning electron microscopy, energy dispersive X-ray, X-ray diffraction, vibrational sample magnetometry, and Fourier transform infrared. The catalytic activity is probed for cross-dehydrogenative coupling of aromatic aldehydes in the presence of tert-butyl hydroperoxide as the oxidant. This catalytic protocol appears as a simple, rather cheap, clean, and efficient practical strategy for the synthesis of symmetrical anhydrides, with proper efficiency (66%). The catalyst can be easily separated from the reaction mixture by an external magnet and reused several times in subsequent reactions, without any measurable loss of its efficiency. Graphic abstract: [Figure not available: see fulltext.]
- Eidi, Esmaiel,Kassaee, Mohamad Z.,Nasresfahani, Zahra
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- Simple preparation of symmetrical carboxylic acid anhydrides by means of Na2CO3/SOCl2
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A convenient and general method for the synthesis of symmetrical carboxylic acid anhydrides using sodium carbonate/thionyl chloride is described. Copyright Taylor & Francis Group, LLC.
- Kazemi,Kiasat,Mombaini
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- Oxidative self-coupling of aldehydes in the presence of CuCl2/TBHP system: Direct access to symmetrical anhydrides
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A simple synthesis of symmetrical anhydrides has been developed. Using tert-butylhydroperoxide (TBHP) as the oxidant and copper(II) chloride as the catalyst in acetonitrile, various aromatic and heteroaromatic aldehydes were reacted to provide symmetrical anhydrides in modest to good yields.
- Saberi, Dariush,Shojaeyan, Fatemeh,Niknam, Khodabakhsh
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- Sc(OTf)3-catalyzed synthesis of anhydrides from twisted amides
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A novel synthesis of anhydrides from twisted amides is reported. Sc(OTf)3 catalysis in the presence of water is used to synthesize anhydrides in one step from amides without external nucleophiles. Mechanistic studies indicate that the coordination of the catalyst is critical to induce the challenging N-C activation step. This process further highlights the utility of twisted amides in organic synthesis. Notably, the reaction indicates that twisted amides based on the glutarimide scaffold are more reactive than carboxylic acid anhydrides under the developed conditions, which opens the door to controlled sequential catalysis through amide N-C bond cleavage.
- Liu, Yongmei,Liu, Ruzhang,Szostak, Michal
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- Diphosphonium fluorosulfonate reagent as a dehydrating agent in organic synthesis
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A facile, one-pot dehydration of organic substrates is afforded by the 'diphosphonium fluorosulfonate' reagent, Ph3P(+)OP(+)Ph3*2SO3F(-).This reagent has been used to convert acids to anhydrides, acid and alcohols to esters, acids and amines to amides and in double dehydrations to form heterocycles.
- Niyogi, Debyani G.,Singh, Sukhjinder,Verma, R. D.
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- Esterification by Redox Dehydration Using Diselenides as Catalytic Organooxidants
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Ortho-functionalized aryl diselenides are catalytic (5.0 mol %) oxidants for the construction of esters from carboxylic acids and alcohols in the presence of stoichiometric triethyl phosphite and dioxygen in air as the terminal redox reagents (redox dehydration conditions). The reaction proceeds through the intermediacy of the anhydride and requires the presence of 10% DMAP to drive the esterification.
- Pickel, Thomas C.,Akondi, Srirama Murthy,Liebeskind, Lanny S.
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- Dabco/SOCl2, mild, and convenient reagent for the preparation of symmetrical carboxylic acid anhydrides
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Various types of carboxylic acids undergo rapid dehydration with 1,4-diazabicyclo[2.2.2]octane, dabco / thionyl chloride, under mild reaction conditions to afford symmetrical acid anhydrides in high isolated yields.
- Kazemi, Foad,Kiasat, Ali Reza
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- Dehydration induced by intramolecular redox character of a stable allylidenetributylphosphorane
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An air and moisture stable P-ylide, dimethyl fluorenylidenetributylphosphoranylidenesuccinate acts as a new type of dehydrating agent for synthesizing acid anhydride, ester, and amide. The ylide is most suitable for inducing these reactions in analogous P-ylides. The reaction is considered to be caused by internal reductive and oxidative nature of the P-ylide.
- Kawamura, Yasuhiko,Sato, Yoshinori,Horie, Tokunaru,Tsukayama, Masao
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- Chiral separation materials based on derivatives of 6-amino-6-deoxyamylose
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In order to develop new type of chiral separation materials, in this study, 6-amino-6-deoxyamylose was used as chiral starting material with which 10 derivatives were synthesized. The amino group in 6-amino-6-deoxyamylose was selectively acylated and then the hydroxyl groups were carbamoylated yielding amylose 6-amido-6-deoxy-2,3-bis(phenylcarbamate)s, which were employed as chiral selectors (CSs) for chiral stationary phases of high-performance liquid chromatography. The resulted 6-amido-6-deoxyamyloses and amylose 6-amido-6-deoxy-2,3-bis(phenylcarbamate)s were characterized by IR, 1H NMR, and elemental analysis. Enantioseparation evaluations indicated that most of the CSs demonstrated a moderate chiral recognition capability. The 6-nonphenyl (6-nonPh) CS of amylose 6-cyclohexylformamido-6-deoxy-2,3-bis(3,5-dimethylphenylcarbamate) showed the highest enantioselectivity towards the tested chiral analytes; the phenyl-heterogeneous (Ph-hetero) CS of amylose 6-(4-methylbenzamido)-6-deoxy-2,3-bis(3,5-dimethylphenylcarbamate) baseline separated the most chiral analytes; the phenyl-homogeneous (Ph-homo) CS of amylose 6-(3,5-dimethylbenzamido)-6-deoxy-2,3-bis(3,5-dimethylphenylcarbamate) also exhibited a good enantioseparation capability among the developed CSs. Regarding Ph-hetero CSs, the enantioselectivity depended on the combination of the substituent at 6-position and that at 2- and 3-positions; as for Ph-homo CSs, the enantioselectivity was related to the substituent at 2-, 3-, and 6-positions; with respect to 6-nonPh CSs, the retention factor of most analytes on the corresponding CSPs was lower than that on Ph-hetero and Ph-homo CSPs in the same mobile phases, indicating π–π interactions did occur during enantioseparation. Although the substituent at 6-position could not provide π–π interactions, the 6-nonPh CSs demonstrated an equivalent or even higher enantioselectivity compared with the Ph-homo and Ph-hetero CSs.
- Gao, Ya-Ya,Zhang, Yu-Hang,Zhang, Shan,Chen, Wei,Bai, Zheng-Wu
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p. 899 - 914
(2021/10/07)
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- Preparation method of symmetric aromatic anhydride compound
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The invention discloses a preparation method of a symmetric aromatic anhydride compound, the preparation method comprises the following steps: dissolving alpha-terpilenol and pyridine in a solvent, adding an aroyl chloride solution, and reacting for 8-16 hours to obtain the symmetric aromatic anhydride compound. The alpha-terpilenol and the aroyl chloride are used as raw materials, and the method has the advantages of being easy to operate, mild in reaction condition, high in safety, simple in technological process and post-treatment, low in cost, high in yield of part of products and the like, and is very beneficial to industrialization.
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Paragraph 0045-0046; 0057-0058
(2021/08/11)
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- PPh3/Selectfluor-Mediated Transformation of Carboxylic Acids into Acid Anhydrides and Acyl Fluorides and Its Application in Amide and Ester Synthesis
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By taking the advantage of PPh3/Selectfluor system, carboxylic acids are efficiently converted into the pivotal intermediates acyloxyphosphonium ions that can selectively react with a second carboxylic acid or fluoride to in situ yield the corresponding acid anhydrides or acyl fluorides. The developed protocol features commercially availabile reagents, no involvement of base, room temperature conditions, and simple experimental procedure. Additionally, various amides or esters are readily achieved, respectively, with the addition of amines or alcohols.
- Yang, Zhen,Chen, Siwei,Yang, Fang,Zhang, Chenxi,Dou, You,Zhou, Qiuju,Yan, Yizhe,Tang, Lin
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p. 5998 - 6002
(2019/08/21)
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- Vilsmeier-Haack reagent mediated synthetic transformations with an immobilized iridium complex photoredox catalyst
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An immobilized iridium complex photocatalyst Ir(ppy)2(PDVB-py) was synthesized by immobilization of the iridium complex onto the nanoporous vinylpyridine-divinylbenzene copolymer (PDVB-py). Its application for the synthesis of amides, nitriles, and anhydrides was reported via reactions under the action of the visible-light-driven in situ generated Vilsmeier-Haack reagent from CBr4 in DMF. The results showed that this heterogeneous photocatalyst has extremely high activity and excellent stability to be recycled five times.
- Zhi, Peng,Xi, Zi-Wei,Wang, Dan-Yan,Wang, Wei,Liang, Xue-Zheng,Tao, Fei-Fei,Shen, Run-Pu,Shen, Yong-Miao
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supporting information
p. 709 - 717
(2019/01/10)
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- PIII-Chelation-Assisted Indole C7-Arylation, Olefination, Methylation, and Acylation with Carboxylic Acids/Anhydrides by Rhodium Catalysis
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Rhodium-catalyzed C7-selective decarbonylative arylation, olefination, and methylation of indoles with carboxylic acids or anhydrides by C?H and C?C bond activation have been developed. Furthermore, C7-acylation products can also be generated selectively at a lower reaction temperature in the developed system. The key to the high reactivity and regioselectivity of this transformation is the appropriate choice of an indole N-PtBu2 chelation-assisted group. This method has many advantages, including easy access and removal of the directing group, the use of cheap and widely available coupling agents, no requirement of an external ligand or oxidant, a broad substrate scope, high efficiency, and the formation of a sole regioisomer.
- Qiu, Xiaodong,Wang, Panpan,Wang, Dingyi,Wang, Minyan,Yuan, Yu,Shi, Zhuangzhi
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supporting information
p. 1504 - 1508
(2019/01/04)
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- Synthesis, biological evaluation and docking study of a new series of di-substituted benzoxazole derivatives as selective COX-2 inhibitors and anti-inflammatory agents
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A new series of substituted-N-(3,4-dimethoxyphenyl)-benzoxazole derivatives 13a–13p was synthesized and evaluated in vitro for their COX (I and II) inhibitory activity, in vivo anti-inflammatory and ulcerogenic potential. Compounds 13d, 13h, 13k, 13l and 13n exhibited significant COX-2 inhibitory activity and selectivity towards COX-2 over COX-1. These selected compounds were screened for their in vivo anti-inflammatory activity by carrageenan induced rat paw edema method. Among these compounds, 13d was the most promising analogs of the series with percent inhibition of 84.09 and IC50 value of 0.04 μM and 1.02 μM (COX-2 and COX-1) respectively. Furthermore, ulcerogenic study was performed and tested compounds (13d, 13h, 13k, 13l) demonstrated a significant gastric tolerance than ibuprofen. Molecular docking study was also performed with resolved crystal structure of COX-2 to understand the binding mechanisms of newly synthesized inhibitors in the active site of COX-2 enzyme and the results were found to be concordant with the biological evaluation studies of the compounds. These newly synthesized inhibitors also showed acceptable pharmacokinetic profile in the in silico ADME/T analyses.
- Kaur, Avneet,Pathak, Dharam P.,Sharma, Vidushi,Wakode, Sharad
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p. 891 - 902
(2018/01/22)
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- Synthesis, biological evaluation and docking study of N-(2-(3,4,5-trimethoxybenzyl)benzoxazole-5-yl) benzamide derivatives as selective COX-2 inhibitor and anti-inflammatory agents
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A series of N-(2-(3,4,5-trimethoxybenzyl)-benzoxazole-5-yl)benzamide derivatives (3a–3n) was synthesized and evaluated for its in vitro inhibitory activity against COX-1 and COX-2. The compounds with considerable in vitro activity (IC50 50 in the range of 0.14–0.69 μM. In vivo anti-inflammatory activity of these six compounds (3b, 3d, 3e, 3h, 3l and 3m) was assessed by carrageenan induced rat paw edema method. The compound 3b (79.54%), 3l (75.00%), 3m (72.72%) and 3d (68.18%) exhibited significant anti-inflammatory activity than standard drug ibuprofen (65.90%). Ulcerogenic activity with histopathological studies was performed, and the screened compounds demonstrated significant gastric tolerance than ibuprofen. Molecular Docking study was also performed with resolved crystal structure of COX-2 to understand the interacting mechanisms of newly synthesized inhibitors with the active site of COX-2 enzyme and the results were found to be in line with the biological evaluation studies of the compounds.
- Kaur, Avneet,Pathak, Dharam P.,Sharma, Vidushi,Narasimhan, Balasubramanian,Sharma, Prateek,Mathur, Rajani,Wakode, Sharad
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p. 191 - 202
(2018/08/23)
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- Synthesis, cyclooxygenase-2 inhibition, anti-inflammatory evaluation and docking study of substituted-n-(3,4,5-trimethoxyphenyl)-benzo[d]oxazole derivatives
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Background: Non-steroidal anti-inflammatory drugs are widely used for many years, but the chronic use of NSAID’s leads to gastric side effects, ulceration and kidney problems. These side effects are due to non-selective inhibition of COX-2 along with COX-1. Therefore, it is imperative to develop novel and selective COX-2 inhibitors. Objective: In this paper wehave synthesized a series of novel hybrids comprising of substituted-N-(3,4,5-trimethoxyphenyl)-benzo[d]oxazole derivatives and screened for the treatment of inflammation. Methods: The structures of the obtained compounds were elucidated by elemental and spectral analysis (ATR-FTIR,1 H NMR,13 C NMR, Mass spectroscopy). All of the compounds were evaluated for cyclooxygenase (COX-1/COX-2) inhibitory activity by in vitro enzymatic assay. The compound which showed COX-2 activity (3a-3e, 3g – 3h, 3k, 3m and 3o) was further screened for in vivo anti-inflammatory activity and ulcerogenic liability. Molecular docking study was also performed with resolved crystal structure of COX-2 to understand the binding mechanism of newly synthesized inhibitors in the active site of COX-2enzyme. Results: The in vitro COX-1 and COX-2 inhibitory studies showed that the synthesized compounds potentially inhibited COX-2 (IC50 = 0.04 – 26.41 μM range) over COX-1 (IC50 = 0.98 – 33.33 μM range). The in vivo studies predicted that compounds 3c (70.9%, 0.6±0.22), 3m (68.1%, 1.9±0.41) and 3o (70.4%, 1.7±0.27) produced more efficacy against carrageenan induced paw edema and less ulcerogenic effect, as compared to standard ibuprofen (65.9%, 2.2±0.44). The results of docking studies were found to be concordant with the biological evaluation studies of the prepared compound. Conclusion: Among all the tested compounds, 2-Chloro-N-(2-(3,4,5-trimethoxyphenyl)-benzo[d]oxazol-5-yl)-benzamide (3c) was the most potent anti-inflammatory agent and has less ulcerogenic potential. This series of compound can be explored more for development of safer and more active anti-inflammatory agents.
- Kaur, Avneet,Wakode, Sharad,Pathak, Dharam P.,Sharma, Vidushi,Shakya, Ashok K.
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p. 660 - 673
(2018/11/06)
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- Versatile Heterogeneous Palladium Catalysts for Diverse Carbonylation Reactions under Atmospheric Carbon Monoxide Pressure
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Herein, we report a versatile carbonylation protocol using heterogeneous Pd0 nanoparticles supported on the metal–organic frameworks (MOFs) MIL-88B-NH2 (Fe/Cr). The synthesis of a vast array of carbonyls, which includes amides, esters, carboxylic acids, and α-ketoamides, was achieved through mono- and dicarbonylation reactions. The selectivity could be controlled simply by tuning the reaction conditions. Superior activity and selectivity were recorded in some cases compared to that achieved with commercial Pd/C. However, the utility of an elaborate catalyst support is questionable and important reactivity and recyclability issues are discussed.
- Vico Solano, Marta,González Miera, Greco,Pascanu, Vlad,Inge, A. Ken,Martín-Matute, Belén
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p. 1089 - 1095
(2018/02/06)
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- TBHP/ n -Bu 4 PBr-Promoted Oxidative Cross-Dehydrogenative Coupling of Aryl Methanols: A Facile Synthesis of Symmetrical Carboxylic Anhydride Derivatives
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A transition-metal-free oxidative cross-dehydrogenative coupling reaction has been developed for the preparation of symmetrical carboxylic anhydrides through self-coupling dual C-O bond formations of aryl methanols. In the presence of a catalytic amount of tetrabutylphosphonium bromide (TBPB) as transfer agent and aqueous tert -butyl hydroperoxide (TBHP) as oxidant and reactant, methylene groups of aryl methanols were efficiently oxidized to C=O and coupled with the peroxide oxygen from TBHP to form a diverse array of symmetrical carboxylic anhydride derivatives.
- Adib, Mehdi,Pashazadeh, Rahim
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supporting information
p. 136 - 140
(2017/12/27)
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- An investigation on practical synthesis of carboxylic acid derivatives using p-toluenesulfonyl chloride
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Carboxylic acid derivatives are well recognized as important class of reagents frequently used in the preparation of a variety of fine or special chemicals such as amides, esters, peptides, drugs, and dyes. Although several methods were developed for the preparation of these compounds, many of them present difficulties, including low yield, high reaction temperature, harsh reaction conditions, tedious work-up, and incompatibility with scale-up. Methods: The synthesis of carboxylic anhydrides is developed through the reaction of carboxylic acids with TsCl in the presence of K2CO3 and acetonitrile as a solvent under ultrasound irradiation and conventional conditions. In addition, one-pot synthesis of acyl azides was carried out in the presence of produced carboxylic anhydrides and the addition of sodium azide under identical condition. Results: A series of carboxylic anhydrides and acyl azides were synthesized using TsCl under ultrasound irradiation and conventional stirring with simple procedure, mild reaction conditions, high yields, and scale-up ability without any restriction. In most cases, the reaction under ultrasound irradiation was better in both yields and the reaction times compared to the conventional method. Conclusion: A convenient method has been developed for the preparation of carboxylic anhydrides and acyl azides under ultrasound irradiation and conventional stirring. The present method is practical and a highly effective alternative for previous reports. The major advantages of this method are: (i) simplicity of the procedure (ii) high yields and high purity of product (iii) scale-up capacity without considerable limitation in conventional system. Under ultrasound irradiation short reaction times as compared to conventional method are observed; yields are comparable to or better than conventional method.
- Eskandari, Parvin,Kazemi, Foad
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p. 431 - 439
(2017/07/24)
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- Anhydrides from aldehydes or alcohols via oxidative cross-coupling
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A novel type of metal-free oxidative cross-coupling for the synthesis of symmetrical and mixed anhydrides from aldehydes or benzylic alcohols has been developed. The aldehydes or alcohols were converted in situ into their corresponding acyl chlorides, which were then reacted with an array of carboxylic acids. The methodology has a general applicability, and was successfully employed to prepare either aromatic or aliphatic symmetrical anhydrides and mixed anhydrides, which are very unstable compounds.
- Gaspa, Silvia,Amura, Ida,Porcheddu, Andrea,De Luca, Lidia
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supporting information
p. 931 - 939
(2017/02/10)
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- Metal-free oxidative self-coupling of aldehydes or alcohols to symmetric carboxylic anhydrides
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A metal-free synthesis of symmetrical anhydrides has been developed starting from aldehydes, both aliphatic and aromatic or primary benzylic alcohols. The reaction occurs at room temperature and makes use of trichloroisocyanuric acid (TCCA) as an oxidant providing the desired carboxylic anhydrides in satisfactory yields.
- Gaspa, Silvia,Porcheddu, Andrea,De Luca, Lidia
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supporting information
p. 2533 - 2536
(2017/06/13)
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- Mechanism of Acylative Oxidation-Reduction-Condensation Reactions Using Benzoisothiazolones as Oxidant and Triethylphosphite as Stoichiometric Reductant
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We previously described a new organocatalytic oxidation-reduction-condensation for amide/peptide construction. The reaction system relies on triethylphosphite as the stoichiometric reductant and organocatalytic benzoisothiazolone/O2 in air as the oxidant. The reaction was assumed to generate catalytic quantities of S-acylthiosalicylamides as electrophiles, which are rapidly intercepted by amine reactants to generate amides/peptides and o-mercaptobenzamides. The latter are then gently reoxidized to the benzoisothiazolones under Cu-catalyzed aerobic conditions to complete the catalytic cycle. To gain a mechanistic understanding, we describe herein our studies of the stoichiometric generation of S-acylthiosalicylamides under oxidation-reduction-condensation conditions from a variety of benzoisothiazolones and carboxylic acids using triethylphosphite as the terminal reductant. These studies have revealed the presence of more than one reaction pathway when benzoisothiazolones react with triethylphosphite (including a rapid, direct deoxygenation of certain classes of benzoisothiazolones by triethylphosphite) and allow the identification of optimal reaction characteristics (benzoisothiazolone structure and solvent) for the generation of thioesters. These explorations will inform our efforts to develop highly effective and robust organocatalytic oxidation-reduction-condensation reactions that are based on the benzoisothiazolone and related motifs.
- Gangireddy, Pavankumar,Patro, Vidyavathi,Lam, Leighann,Morimoto, Mariko,Liebeskind, Lanny S.
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p. 3513 - 3529
(2017/04/11)
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- Acid anhydrides and the unexpected N,N-diethylamides derived from the reaction of carboxylic acids with Ph3P/I2/Et3N
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The formation of acid anhydrides from the phosphorous-mediated activation of carboxylic acids was investigated. Under various systems, activation of benzoic acid in the presence of base led to the formation of benzoic anhydride at different rates depending on the reactivity of the reagents. Using the Ph3P-I2/Et3N combination, most aryl acids were converted into the corresponding anhydrides in high yields within 5-10 min. However, for nitro-substituted derivatives, unexpectedly, N,N-diethylamides were isolated without anhydride formation. These results indicated the pronounced effect of substituents in governing these potential side reactions which can significantly affect the yields of acylation reactions promoted by phosphonium species.
- Phakhodee, Wong,Duangkamol, Chuthamat,Wangngae, Sirilak,Pattarawarapan, Mookda
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supporting information
p. 325 - 328
(2016/01/12)
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- Metal-free cross-dehydrogenative coupling of aryl aldehydes to give symmetrical carboxylic anhydrides promoted by the TBHP/nBu4PBr system
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A novel, efficient, and metal-free dual C–O bond formation reaction for the synthesis of carboxylic anhydrides from aryl aldehydes via cross-dehydrogenative coupling is described. Heating a mixture of aromatic aldehydes and an aqueous solution of tert-butyl hydroperoxide as oxidant in the presence of catalytic nBu4PBr in chlorobenzene at 80?°C for 3?h afforded the corresponding carboxylic anhydrides in good to excellent yields.
- Adib, Mehdi,Pashazadeh, Rahim,Rajai-Daryasarei, Saideh,Mirzaei, Peiman,Jamal Addin Gohari, Seyed
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supporting information
p. 3071 - 3074
(2016/07/06)
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- Facile and direct synthesis of symmetrical acid anhydrides using a newly prepared powerful and efficient mixed reagent
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An efficient mixed reagent for direct synthesis of symmetrical carboxylic anhydrides from carboxylic acids has been prepared. Carboxylic acids are converted to anhydrides using triphenylphosphine/ trichloroisocyanuric acid under mild reaction conditions at room temperature. Short reaction time, excellent yields of products, low cost, availability of reagents, simple experimental procedure, and easy work-up of the products are the main advantages of the presented method.
- Rouhi-Saadabad, Hamed,Akhlaghinia, Batool
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p. 479 - 485
(2015/01/30)
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- Synthesis of acylsilanes by copper(I)-catalyzed addition of silicon nucleophiles onto acid derivatives
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The transition metal-catalyzed transfer of silicon nucleophiles onto various electrophiles has recently gained considerable attention, due to the now readily available silicon pro-nucleophiles such as silylboronates. Our interest lies in the addition of such species to acid derivatives for the generation of acylsilanes. We report herein an efficient method to synthesize these compounds, starting from easy-to-form anhydrides, with very good yields. Copyright
- Cirriez, Virginie,Rasson, Corentin,Riant, Olivier
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supporting information
p. 3137 - 3140
(2013/12/04)
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- Carboxylic acid anhydrides via Pd-catalyzed carbonylation of aryl halides at atmospheric CO pressure
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A convenient method has been developed, which allows for the direct transformation of aryl iodides into the corresponding carboxylic acid anhydrides via Pd-catalyzed carbonylation under atmospheric CO pressure. The Royal Society of Chemistry 2012.
- Li, Yang,Xue, Dong,Wang, Chao,Liu, Zhao-Tie,Xiao, Jianliang
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supporting information; experimental part
p. 1320 - 1322
(2012/02/04)
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- Efficient and convenient synthesis of symmetrical carboxylic anhydrides from carboxylic acids with sulfated zirconia by phase transfer catalysis
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An efficient and convenient procedure for the synthesis of symmetrical carboxylic anhydrides from carboxylic acids with sulfated zirconia by PEG-1000 phase transfer catalysis has been developed. The reactions proceeded under mild and solvent-free conditions to provide the carboxylic anhydrides in good to excellent yields. The product can be isolated by a simple extraction with organic solvent, and the catalyst system can be recycled or reused without any significant loss of catalytic activity.
- Hu, Yu Lin,Zhao, Xing E.,Lu, Ming
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experimental part
p. 255 - 262
(2012/04/17)
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- A mild, clean, and simple synthesis of symmetrical carboxylic anhydrides from carboxylic acides using a polymer supported tosyl chloride
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The use of polymeric reagents simplifies routine acylation of carboxylic acid because it eliminates the traditional purification. We describe the use of readily available cross-linked poly(4-vinylpyridine) supported tosyl chloride, [P4VP].TsCl, in the suspended solution phase synthesis of symmetrical anhydrides from carboxylic acids in the presence of K2CO3 in high yields and purity. The products can be obtained by filtration and evaporation of the solvent.
- Zarchi, M. A. Karimi,Mirjalili,Kahrizsangi, Z. Shamsi,Tayefi
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experimental part
p. 455 - 460
(2010/08/20)
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- 5H-3-oxa-Octafluoropentanesulfonyl fluoride: a novel and efficient condensing agent for esterification, amidation and anhydridization
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The use of 5H-3-oxa-octafluoropentanesulfonyl fluoride (HCF2CF2OCF2CF2SO2F) as a novel and efficient condensing reagent for esterification of carboxylic acids with alcohols and amidation of carboxylic acids with amines in the presence of 1,3-diazabicyclo[5.4.0]-undec-7-ene (DBU) is reported. HCF2CF2OCF2CF2SO2F cannot serve as a condensing agent for anhydridization of carboxylic acids, however, HCF2CF2OCF2CF2SO2F/(CH3)3SiCN system can mediate anhydridization of some aromatic carboxylic acids.
- Yan, Zhaohua,Tian, Weisheng,Zeng, Fanrong,Dai, Yanfeng
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experimental part
p. 2727 - 2729
(2009/09/06)
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- Triphenylphosphine oxide supported on non-cross-linked maleimide-styrene copolymer: application as a novel Hendrickson reagent
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A new triphenylphosphine oxide reagent linked to a linear maleimide-styrene copolymer is synthesized. This phosphine-bound copolymer is converted to copolymer-supported triphenylphosphine ditriflate as a novel Hendrickson reagent by treatment with triflic anhydride. This reacts rapidly in various dehydration reactions such as anhydride, ester and amide formation. This linear and soluble support is also easily recovered and recycled several times without loss of efficiency.
- Mahdavi, Hossein,Amani, Javad
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p. 2204 - 2207
(2008/09/18)
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- Investigation of the Yamaguchi esterification mechanism. Synthesis of a Lux-S enzyme inhibitor using an improved esterification method
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(Chemical Equation Presented) A one-pot procedure for the regioselective synthesis of aliphatic esters is described. This was a result of a study on mixed aliphatic-aromatic anhydrides. The data suggest that during the Yamaguchi esterification reaction, a symmetric aliphatic anhydride is produced in situ, which upon reaction with an alcohol yields the ester. We confirmed that benzoyl chloride could be used instead of the sterically hindered Yamaguchi acid chloride. This method was successfully applied in the synthesis of Lux-S aspartic acid inhibitor.
- Dhimitruka, Ilirian,SantaLucia Jr., John
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- Substrate activity screening: A fragment-based method for the rapid identification of nonpeptidic protease inhibitors
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A new fragment-based method for the rapid development of novel and distinct classes of nonpeptidic protease inhibitors, Substrate Activity Screening (SAS), is described. This method consists of three steps: (1) a library of N-acyl aminocoumarins with diverse, low molecular weight N-acyl groups is screened to identify protease substrates using a simple fluorescence-based assay, (2) the identified N-acyl aminocoumarin substrates are optimized by rapid analogue synthesis and evaluation, and (3) the optimized substrates are converted to inhibitors by direct replacement of the aminocoumarin with known mechanism-based pharmacophores. The SAS method was successfully applied to the cysteine protease cathepsin S, which is implicated in autoimmune diseases. Multiple distinct classes of nonpeptidic substrates were identified upon screening an N-acyl aminocoumarin library. Two of the nonpeptidic substrate classes were optimized to substrates with >8000-fold improvements in cleavage efficiency for each class. Select nonpeptidic substrates were then directly converted to low molecular weight, novel aldehyde inhibitors with nanomolar affinity to cathepsin S. This study demonstrates the unique characteristics and merits of this first substrate-based method for the rapid identification and optimization of weak fragments and provides the framework for the development of completely nonpeptidic inhibitors to many different proteases.
- Wood, Warren J. L.,Patterson, Andrew W.,Tsuruoka, Hiroyuki,Jain, Rishi K.,Ellman, Jonathan A.
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p. 15521 - 15527
(2007/10/03)
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- ZnCl2-mediated synthesis of carboxylic anhydrides using 2-acyl-4,5-dichloropyridazin-3(2H)-ones
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ZnCl2 is an efficient catalyst for synthesis of carboxylic acid anhydride from 2-acyl-4,5-dichloropyridazin-3(2H)-ones. Treatment of 2-acyl-4,5-dichloropyridazin-3(2H)-ones with ZnCl2 (0.5 equivalents) and air in refluxing dry THF or
- Park, Yong-Dae,Kim, Jeum-Jong,Kim, Ho-Kyun,Cho, Su-Dong,Kang, Young-Jin,Park, Ki Hun,Lee, Sang-Gyeong,Yoon, Yong-Jin
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p. 371 - 378
(2007/10/03)
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- Novel polymer-supported coupling/dehydrating reagents for use in organic synthesis
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Two novel dehydrating reagents 3 and 4, based on a phosphonium anhydride and an oxyphosphonium triflate respectively, were prepared by reaction of the corresponding polymer-supported phosphine oxides with triflic anhydride. Reagent 3, based on the novel phosphorus heterocycle 1,1,3,3-tetraphenyl-2-oxa-1,3- diphospholanium bis(trifluoromethanesulfonate), was found to be a useful reagent for ester and amide formation. A wide range ofcoupling/dehydration-type reactions, such as ester, amide, anhydride, peptide, ether and nitrile formation, were performed in high yield using the more readily prepared polymer-supported triphenylphosphine ditrinate 4, which was easily recovered and re-used several times without loss of efficiency. With primary alcohols, both reagents 3 and 4 provide an alternative to the Mitsunobu reaction, where the use of azodicarboxylates and chromatography to remove the phosphine oxide by-product can be avoided. The use of 4-dimethylaminopyridine allowed the esterification of secondary alcohols with 4 to proceed in high yield but with retention of configuration.
- Fairfull-Smith, Kathryn E.,Jenkins, Ian D.,Longhlin, Wendy A.
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p. 1979 - 1986
(2007/10/03)
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- Polymer-supported triphenylphosphine ditriflate: A novel dehydrating reagent
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A new type of polymeric dehydrating reagent, readily prepared by the treatment of polymer-supported triphenylphosphine oxide with triflic anhydride, was found to be effective in a variety of dehydration reactions such as ester and amide formation; the polymer-supported triphenylphosphine oxide was easily recovered and reused several times without the loss of activity.
- Elson, Kathryn E.,Jenkins, Ian D.,Loughlin, Wendy A.
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p. 2491 - 2493
(2007/10/03)
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- A Cheap, Simple and Efficient Method for the Preparation of Symmetrical Carboxylic Acid Anhydrides
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A manipulatively simple and facile one-pot procedure for the synthesis of symmetrical anhydride is reported. Treatment of carboxylic acids with tosyl chloride in K2CO3 media under solvent free conditions gives the corresponding anhydrides in good to excellent yields in a short reaction time via carboxylic sulfonic anhydride as the key intermediate.
- Kazemi, Foad,Sharghi, Hashem,Nasseri, Mohammad Ali
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p. 205 - 207
(2007/10/03)
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- Facile synthesis of carboxylic anhydrides using 4,5-dichloro-2-[(4-nitrophenyl)sulfonyl]pyridazin-3(2H)-one
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A novel and facile synthesis of carboxylic anhydrides from carboxylic acid using 4,5-dichloro-2-[(4-nitrophenyl)sulfonyl]pyridazin-3(2H)-one (2) is presented. Treatment of aliphatic or aromatic carboxylic acids with 2 in the presence of base in organic solvents gave the corresponding anhydrides in good or excellent yields.
- Kim, Jeum-Jong,Park, Yong-Dae,Song Lee, Woo,Cho, Su-Dong,Yoon, Yong-Jin
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p. 1517 - 1520
(2007/10/03)
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- Synthesis of unsymmetrical ketones by palladium-catalyzed cross-coupling reaction of carboxylic anhydrides with organoboron compounds
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On the basis of fundamental studies on oxidative addition of carboxylic anhydrides to zerovalent palladium complexes to yield acyl(carboxylato)bis(tertiary phosphine)palladium(II) complexes and their reactions with organoboronic acids to yield ketones, a novel catalytic process has been developed. This converts carboxylic anhydrides and organoboron compounds into ketones catalyzed by palladium complexes under mild conditions. The process provides a general, versatile, synthetic method to produce various symmetrical and unsymmetrical ketones with aromatic, aliphatic, and heterocyclic groups. The catalytic cycle is proposed to comprise (a) oxidative addition of a carboxylic anhydride to produce an acyl(carboxylato)palladium intermediate, (b) transmetallation with an organoboron compound to give an acyl(organo)palladium intermediate, and (c) its reductive elimination to yield a ketone. Not only homogeneous catalyst systems but also heterogeneous systems were found to give ketones under mild conditions.
- Kakino, Ryuki,Yasumi, Sayaka,Shimizu, Isao,Yamamoto, Akio
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p. 137 - 148
(2007/10/03)
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- An efficient and simple procedure for preparation of esters and anhydrides from acid chlorides in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) under solvent-free conditions
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A manipulatively one-pot and rapid method for the synthesis of aliphatic and aromatic ester and anhydride from acid chloride and alcohol or potassium salt of carboxylic acid under solvent-free conditions is reported. The reaction has been carried out in excellent yield and short reaction time in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) under solvent-free conditions.
- Hajipour,Mazloumi
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- A thermal fragmentation of 1,2,4-oxadiazole-4-oxides to nitriles and nitrosocarbonyls
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1,2,4-Oxadiazole-4-oxides undergo clean thermal cleavage in refluxing chlorobenzene or xylene to nitriles and nitrosocarbonyl intermediates, which are either trapped with suitable olefins to afford ene adducts or dimerize and rearrange to anhydrides. (C) 2000 Elsevier Science Ltd.
- Quadrelli,Campari,Mella,Caramella
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p. 2019 - 2022
(2007/10/03)
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- A facile synthesis of acid anhydrides
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A facile synthesis of symmetric and unsymmetric acid anhydrides using phase-transfer catalysis is described. By this method different types of anhydrides can be obtained in high yields under mild conditions even on microscale levels.
- Dubey,Kumar, R. Vinod
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- Solid-liquid phase transfer and cobalt or palladium complex catalyzed synthesis of anhydrides from acyl chlorides
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Acyl chloride can efficiently be converted into anhydride under solid liquid phase transfer catalysis by using bis(triphenylphosphine)cobalt dichloride or bis (triphenylphospine)palladium dichloride as catalyst.
- Wang,Hu,Cui
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p. 3261 - 3268
(2007/10/02)
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- COBALT(II) CHLORIDE CATALYZED SYNTHESES OF ACID ANHYDRIDES FROM ACID CHLORIDES
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Acid anhydrides were synthesized by reacting acid chlorides with carboxylic acids in the presence of catalytic quantities of cobalt(II) chloride.
- Srivastava, Rajiv R.,Kabalka, George W.
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p. 593 - 594
(2007/10/02)
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