- Ynamide-Mediated Intermolecular Esterification
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An ynamide-mediated one-pot, two-step intermolecular esterification via the condensation of carboxylic acids with nucleophilic hydroxyl species was reported. A broad substrate scope with respect to carboxylic acids, alcohols, and phenols was observed. The α-acyloxyenamide intermediates formed by the addition of carboxylic acids to ynamides proved to be effective acylating reagents for the esterification of alcohol and phenol derivatives with the assistance of base catalysis. Notably, the racemization of the α-chiral center of carboxylic acids can be avoided.
- Wang, Xuewei,Yang, Yang,Zhao, Yongli,Wang, Sheng,Hu, Wenchang,Li, Jinmei,Wang, Zihao,Yang, Fengling,Zhao, Junfeng
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p. 6188 - 6194
(2020/05/26)
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- Anhydrous Conditions Enable the Catalyst-Free Carboxylation of Aromatic Alkynes with CO2 under Mild Conditions
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The direct carboxylation of aromatic alkynes with CO2, a cheap and widely available C1 source, is the most attractive method for the synthesis of carboxylic acids. Here we show that direct carboxylation of terminal alkynes can be simply performed in near-quantitative yield in four hours with anhydrous Cs2CO3 under mild conditions without need of a metal catalyst.
- Bobbink, Felix D.,Dyson, Paul J.,Mazzanti, Marinella,Toniolo, Davide
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- Cu-MOF-Catalyzed Carboxylation of Alkynes and Epoxides
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The catalytic activity of copper-containing heterogeneous catalysts, in particular metal-organic frameworks, zeolites, and alumina-supported nanoparticles, in the carboxylation of terminal alkynes and oxiranes has been evaluated. Temperature dependences of these reactions have been studied.
- Beletskaya, I. P.,Bondarenko, G. N.,Ganina, O. G.,Isaeva, V. I.,Kustov, L. M.
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p. 1813 - 1820
(2020/02/03)
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- 3 - Aryl methylacetylene acid and 3 - aryl methylacetylene ester preparation method of compound (by machine translation)
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The invention relates to a 3 - aryl methylacetylene acid compound preparation method: formula (I) shown phenylacetylene compound with carbon dioxide under the action of alkali, in solvent dimethyl sulfoxide in 40 - 70 °C under reaction, as shown in formula (II) of the 3 - aryl methylacetylene acid compounds, more than normal pressure of the body reaction in water-free, oxygen-free inert atmosphere, the reaction route is as follows: Wherein R1 Selected from hydrogen, alkyl, alkoxy, phenyl, nitro or halogen. The invention further provides a 3 - aryl methylacetylene ester preparation method of compound: adopting the above-mentioned method of the formula (II) is shown in the 3 - aryl methylacetylene acid compound, then adding the halogenated hydrocarbon or tosylates, after the in-situ reaction of the formula (III) is shown in the 3 - aryl methylacetylene ester compound: Wherein R2 Is selected from alkyl, benzyl or allyl. The method of the invention does not need to transition metal or rare earth metal catalyst, normal pressure reaction, mild condition, pervasive good substrate. (by machine translation)
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Paragraph 0148; 0149; 0150
(2018/10/19)
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- Encapsulation of Silver Nanoparticles in an Amine-Functionalized Porphyrin Metal–Organic Framework and Its Use as a Heterogeneous Catalyst for CO2 Fixation under Atmospheric Pressure
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A new porphyrin-based compound, [Zn3(C40H24N8)(C20H8N2O4)2(DEF)2](DEF)3 (1; DEF=N,N-diethylformamide), has been synthesized by employi
- Dutta, Gargi,Jana, Ajay Kumar,Singh, Dheeraj Kumar,Eswaramoorthy,Natarajan, Srinivasan
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supporting information
p. 2677 - 2684
(2018/08/11)
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- Alkynylation of Csp2 (O)–H Bonds Enabled by Photoredox-Mediated Hydrogen-Atom Transfer
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The development of new hydrogen-atom transfer (HAT) strategies within the framework of photoredox catalysis is highly appealing for its power to activate a desired C?H bond in the substrate leading to its selective functionalization. Reported here is the first photoredox-mediated hydrogen-atom transfer method for the efficient synthesis of ynones, ynamides, and ynoates with high regio- and chemoselectivity by direct functionalization of Csp2 (O)?H bonds. The broad synthetic application of this method has been demonstrated by the selective functionalization of C(O)?H bonds within complex molecular scaffolds.
- Mukherjee, Satobhisha,Garza-Sanchez, R. Aleyda,Tlahuext-Aca, Adrian,Glorius, Frank
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p. 14723 - 14726
(2017/10/18)
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- Cluster-based MOFs with accelerated chemical conversion of CO2 through C-C bond formation
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Investigations on metal-organic frameworks (MOFs) as direct catalysts have been well documented, but direct catalysis of the chemical conversion of terminal alkynes and CO2 as chemical feedstock by MOFs into valuable chemical products has never
- Xiong, Gang,Yu, Bing,Dong, Jie,Shi, Ying,Zhao, Bin,He, Liang-Nian
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supporting information
p. 6013 - 6016
(2017/07/10)
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- Copper(0) Nanoparticles Supported on Al2O3 as Catalyst for Carboxylation of Terminal Alkynes
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Abstract: The copper particles, supported on Al2O3 were for the first time used as heterogeneous, highly active, easily available, and recyclable copper catalyst of direct carboxylation of various terminal alkynes with CO2
- Bondarenko, Grigoriy N.,Dvurechenskaya, Ekaterina G.,Magommedov, Eldar Sh.,Beletskaya, Irina P.
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p. 2570 - 2580
(2017/09/06)
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- Effective Synthesis of Benzyl 3-Phenylpropiolates Via Copper(I)-Catalyzed Esterification of Alkynoic Acids with Benzyl Halides under Ligand-Free Conditions
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We developed an efficient way to prepare benzyl 3-phenylpropiolates via copper-catalyzed coupling between corresponding benzyl halides and alkynoic acids under ligand-free condition. This methodology is also suitable for aromatic and α,β-unsaturated acids. The desired esters could be obtained in good yields.
- Mao, Jincheng,Yang, Xiaojiang,Yan, Hong,He, Yue,Li, Yongming,Zhao, Jinzhou
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p. 886 - 892
(2016/04/20)
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- Silver tungstate: A single-component bifunctional catalyst for carboxylation of terminal alkynes with CO2 in ambient conditions
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Silver tungstate was successfully developed as a bifunctional catalyst for the ligand-free carboxylation of various terminal alkynes with electron-withdrawing or electron-donating groups under atmospheric pressure of carbon dioxide (CO2) at room temperature. In this protocol, dual activation - i.e., the terminal alkyne activated by silver, and CO2 activation by the tungstate anion - was verified using nuclear magnetic resonance spectroscopy, and means that this reaction can be run under ambient conditions. Notably, this protocol can be applied to the preparation of a phenylacrylate derivative by a cascade reaction using phenylacetylene, CO2 and benzylamine as starting materials.
- Guo, Chun-Xiang,Yu, Bing,Xie, Jia-Ning,He, Liang-Nian
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supporting information
p. 474 - 479
(2018/04/16)
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- Copper(I)-based ionic liquid-catalyzed carboxylation of terminal alkynes with CO2 at atmospheric pressure
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An ionic liquid containing copper(I) proved to be an effective homogeneous catalyst for the carboxylation of terminal alkynes with ambient CO2. This developed procedure needs no external ligands and terminal alkynes with various groups proceeded smoothly at atmospheric CO2 pressure and room temperature. Interestingly, the ILs containing copper(I) in both the anion and the cation showed much higher activity in comparison with the counterparts incorporating copper(I) solely in the form of halocuprate, that is, copper(I) in the anion. Especially, activated effect of the terminal alkyne by the ionic liquid was also validated by the NMR technique.
- Xie, Jia-Ning,Yu, Bing,Zhou, Zhi-Hua,Fu, Hong-Chen,Wang, Ning,He, Liang-Nian
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supporting information
p. 7059 - 7062
(2015/11/27)
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- Copper(I)@carbon-catalyzed carboxylation of terminal alkynes with CO2 at atmospheric pressure
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Activated carbon supported CuBr was found to be an efficient catalyst for the carboxylation of terminal alkynes under atmospheric pressure of CO2 using ethylene carbonate as solvent at 80 °C for only 2 h, as verified with 13CO2. Various terminal alkynes could react smoothly with CO2 and organic halides under the reaction conditions to afford the corresponding carboxylic esters. In addition, the catalyst can be easily recovered and reused at least five times without significant loss of activity.
- Yu, Bing,Xie, Jia-Ning,Zhong, Chun-Lai,Li, Wei,He, Liang-Nian
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p. 3940 - 3944
(2015/11/11)
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- Carboxylation of terminal alkynes at ambient CO2 pressure in ethylene carbonate
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The CuI-catalyzed carboxylation of terminal alkynes with CO2 and alkyl halides using ethylene carbonate as the solvent under mild conditions was studied. DFT calculations reveal that the energy barrier for CO2 insertion into the sp-h
- Yu, Bing,Diao, Zhen-Feng,Guo, Chun-Xiang,Zhong, Chun-Lai,He, Liang-Nian,Zhao, Ya-Nan,Song, Qing-Wen,Liu, An-Hua,Wang, Jin-Quan
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p. 2401 - 2407
(2013/09/12)
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- Synthesis of α,β-alkynyl esters and unsymmetrical maleate esters catalyzed by pd/c; An efficient phosphine-free catalytic system for oxidative alkoxycarbonylation of terminal alkynes
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Pd/C-catalyzed oxidative alkoxycarbonylation of terminal alkynes using alcohols in the presence of tetrabutylammonium iodide under CO/O2 (5:1 atm) has been investigated. The desired α,β-alkynyl esters and unsymmetrical maleate esters are formed in good to excellent yields under different reaction conditions. The present protocol eliminates the use of phosphine ligands and has straightforward catalyst recovery. The catalyst was recycled up to six times without significant loss of catalytic activity. Georg Thieme Verlag Stuttgart . New York.
- Gadge, Sandip T.,Bhanage, Bhalchandra M.
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supporting information
p. 981 - 986
(2013/06/27)
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- Carboxylation of alkynylsilanes with carbon dioxide mediated by cesium fluoride in DMSO
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The facile syntheses of a variety functionalized propiolic acids were achieved by carboxylation of alkynylsilanes with carbon dioxide mediated by cesium fluoride under ambient conditions. This journal is The Royal Society of Chemistry 2013.
- Yonemoto-Kobayashi, Misato,Inamoto, Kiyofumi,Tanaka, Yoshiyuki,Kondo, Yoshinori
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supporting information
p. 3773 - 3775
(2014/03/21)
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- CuII-exchanged montmorillonite K10 clay-catalyzed direct carboxylation of terminal alkynes with carbon dioxide
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A new, simple and straight-forward protocol for direct carboxylation of terminal alkynes has been developed using CuII-montmorillonite K10 clay as a heterogeneous catalyst and CO2 as the C1 carbon feedstock. Also coupling of terminal alkynes with CO2 (1 atm) in the presence of alkyl halides has been achieved under the same reaction conditions, thereby providing access to a variety of functionalized alkyl-2-alkynoates in high yields.
- Aher, Ravindra D.,Gade, Madhuri H.,Reddy, R. Santhosh,Sudalai, Arumugam
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p. 1325 - 1329,5
(2020/08/31)
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- Synthesis of tert-butyl peroxyacetals from benzyl, allyl, or propargyl ethers via iron-promoted C-H bond functionalization
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When benzyl, allyl, and propargyl ethers were treated with tert-butyl hydroperoxide and a catalytic amount of iron(III) acetylacetonate, tert-butyl peroxyacetals were produced in good to excellent yields, via C-H bond functionalization. This method is also applicable to ethylene acetals of unsaturated aldehydes to give peroxyorthoesters.
- Iwata, Satoshi,Hata, Takeshi,Urabe, Hirokazu
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supporting information
p. 3480 - 3484
(2013/02/22)
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- A copper-based catalytic system for carboxylation of terminal alkynes: Synthesis of alkyl 2-alkynoates
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An efficient coupling of terminal alkynes and CO2 in the presence of alkyl halides can be achieved under ambient conditions using a copper/phosphine catalyst system, providing facile access to a variety of functionalised alkyl 2-alkynoates.
- Inamoto, Kiyofumi,Asano, Narumi,Kobayashi, Koji,Yonemoto, Misato,Kondo, Yoshinori
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supporting information; experimental part
p. 1514 - 1516
(2012/03/22)
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- N-Heterocyclic carbene-catalyzed oxidations
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N-Heterocyclic carbenes catalyze the oxidation of allylic and benzylic alcohols as well as saturated aldehydes to esters with manganese(IV) oxide in excellent yields. A variety of esters can be synthesized, including protected carboxylates. The oxidation proceeds under mild conditions, with low loadings of a simple triazolium salt pre-catalyst in the presence of base. Substrates containing potentially epimerizable centers are oxidized while preserving stereochemical integrity. The acyl triazolium intermediate generated under catalytic conditions can be employed as a chiral acylating agent in the desymmetrization of meso-diols.
- Maki, Brooks E.,Chan, Audrey,Phillips, Eric M.,Scheidt, Karl A.
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experimental part
p. 3102 - 3109
(2009/09/05)
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- Tandem oxidation of allylic and benzylic alcohols to esters catalyzed by N-heterocyclic carbenes
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(Chemical Equation Presented) N-Heterocyclic carbenes catalyze the oxidation of allylic, propargylic, and benzylic alcohols to esters with manganese(IV) oxide in excellent yields. A variety of ester derivatives can be synthesized, including protected carboxylates. This one-pot tandem oxidation represents the first organocatalytic oxidation of alcohols to esters. Saturated esters can also be accessed from aldehydes using this method. Through the utilization of a chiral catalyst, the acyl-heteroazolium intermediate becomes a chiral acylating agent, which can desymmetrize meso-1,2-diols.
- Maki, Brooks E.,Chan, Audrey,Phillips, Eric M.,Scheidt, Karl A.
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p. 371 - 374
(2007/10/03)
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- Palladium-catalyzed oxidative carbonylation of 1-alkynes into 2-alkynoates with molecular oxygen as oxidant
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A new preparative method to produce alkyl 2-alkynoates from 1-alkynes in alcohol under atmospheric pressure of CO at room temperature was developed with palladium-phosphine catalysts, using molecular oxygen as an oxidant. On the basis of the behavior of model complexes such as methoxycarbonylpalladium and alkynylpalladium complexes, we propose a mechanism accounting for the catalytic carbonylation of alkynes through an intermediate having the both methoxycarbonyl and alkynyl ligands that liberates methyl 2-alkynoates and a Pd(0) species on reductive elimination. The oxidation of Pd(0) to Pd(II) species in the presence of a halide ion was confirmed to proceed cleanly with molecular oxygen as the oxidant. On the basis of the findings on homogeneous catalysts, a heterogeneous catalytic system using Pd/C has also been developed.
- Izawa, Yusuke,Shimizu, Isao,Yamamoto, Akio
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p. 2033 - 2045
(2007/10/03)
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- Palladium-catalyzed carbonylation of terminal acetylenes: A new method for synthesis of acetylenecarboxylates
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Acetylenecarboxylates were easily prepared via palladium bromide-catalyzed carbonylation of terminal acetylenes in fair to good yields.
- Li,Jiang,Chen
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p. 199 - 202
(2007/10/03)
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- Method for producing 2-alkynoic acid esters
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PCT No. PCT/EP98/02021 Sec. 371 Date Oct. 13, 1999 Sec. 102(e) Date Oct. 13, 1999 PCT Filed Apr. 7, 1998 PCT Pub. No. WO98/46555 PCT Pub. Date Oct. 22, 1998A process for preparing 2-alkynoic esters of the general formula (I),R1-O-CO-C 3BOND C-R2(I)in whic
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- Palladium-catalyzed coupling of alkynes with chloroformates to form alkynecarboxylic acid esters
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The preparation of alkynecarboxylic acid esters, which are versatile building blocks for the synthesis of heterocyclic compounds, is described by means of the, palladium-catalyzed coupling of alkynes with chloroformates for the first time. The Royal Society of Chemistry 1999.
- Boettcher, Arnd,Becker, Heike,Brunner, Melanie,Preiss, Thomas,Henkelmann, Jochem,De Bakker, Christel,Gleiter, Rolf
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p. 3555 - 3556
(2007/10/03)
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