- N-Heterocyclic carbene-nitrogen molybdenum catalysts for utilization of CO2
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Three new N-heterocyclic carbene-nitrogen molybdenum complex was synthesized, and its catalytic activity was evaluated in the cycloaddition of epoxides with CO2. The molybdenum complex combined with tetrabutyl ammonium iodide (TBAI) resulted in a catalytic system for efficient conversion of a wide range of terminal and internal epoxides under 80 °C and 5–7 bar pressure for CO2. The cooperative catalysis mechanism between molybdenum complex and TBAI was elucidated, in which molybdenum complex was used as Lewis acid, and TBAI was employed as nucleophilic reagent. In addition, the NHC-Mo catalytic system was also successfully applied for the direct carboxylation of terminal alkynes with CO2.
- Chen, Fei,Tao, Sheng,Liu, Ning,Dai, Bin
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- Organocatalytic Strategy for the Fixation of CO2via Carboxylation of Terminal Alkynes
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An organocatalytic strategy for the direct carboxylation of terminal alkynes with CO2 has been developed. The combined use of a bifunctional organocatalyst and Cs2CO3 resulted in a robust catalytic system for the preparation of a range of propiolic acid derivatives in high yields with broad substrate scope using CO2 at atmospheric pressure under mild temperatures (60 °C). This work has demonstrated that this organocatalytic method offers a competitive alternative to metal catalysis for the carboxylation of terminal alkynes and CO2. In addition, this protocol was suitable for the three-component carboxylation of terminal alkynes, alkyl halides, and CO2.
- Shi, Jun-Bin,Bu, Qingqing,Liu, Bin-Yuan,Dai, Bin,Liu, Ning
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p. 1850 - 1860
(2021/01/14)
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- Microwave-assisted fabrication of a mixed-ligand [Cu4(μ3-OH)2]-cluster-based metal–organic framework with coordinatively unsaturated metal sites for carboxylation of terminal alkynes with carbon dioxide
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The development of efficient and stable metal–organic framework (MOF) catalysts with coordinatively unsaturated metal sites for modern organic synthesis is greatly important. Herein, a robust [Cu4(μ3-OH)2]-cluster-based MOF (Cu-MOF) with a mixed-ligand system was successfully fabricated by a microwave-assisted method under mild conditions. The as-prepared Cu-MOF catalyst possessing unsaturated Cu (II) sites exhibited excellent catalytic activity toward the direct carboxylation of 1-ethynylbenzene with CO2, and various propiolic acid derivatives were synthesized in moderate to good yields under optimized reaction conditions. Furthermore, the catalyst remained stable and could be easily recycled for five sequential runs without incredible decrease in catalytic efficiency.
- Wang, Wen-Jing,Sun, Zhong-Hua,Chen, Sheng-Chun,Qian, Jun-Feng,He, Ming-Yang,Chen, Qun
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- Oxidant- and additive-free simple synthesis of 1,1,2-triiodostyrenes by one-pot decaroboxylative iodination of propiolic acids
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A metal- and oxidant-free facile synthesis of a range of 1,1,2-triiodostryrene derivatives has been developed which utilizes a simple decarboxylative triiodination of propiolic acids using molecular iodine and sodium acetate in a one-pot manner. Electron-
- Ghosh, Subhankar,Ghosh, Rajat,Chattopadhyay, Shital K.
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supporting information
(2020/09/15)
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- Visible light induced 3-position-selective addition of arylpropiolic acids with ethersviaC(sp3)-H functionalization
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Although the 2-position-selective decarboxylative coupling or addition of arylpropiolic acids with cyclic ethers has been intensively investigated, selective functionalization of arylpropiolic acids at the 3-position is still a big challenge. Herein, an i
- Luo, Jun,Wan, Zi-Juan,Yuan, Xiao-Feng
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supporting information
p. 3258 - 3262
(2020/05/14)
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- Carboxylation of terminal alkynes promoted by silver carbamate at ambient pressure
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Transition metal carbamates constitute a class of compounds with unique properties, however their catalytic potential has been sparingly explored so far. The easily available silver N,N-dimethylcarbamate, Ag(O2CNMe2), worked as a catalyst in the carboxylation reaction of terminal alkynes with CO2 at atmospheric pressure. Different reaction parameters (solvent, base, temperature, time and the amount of catalyst) were investigated in order to establish the optimal conditions.
- Bresciani, Giulio,Marchetti, Fabio,Pampaloni, Guido
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p. 10821 - 10825
(2019/07/15)
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- Rhodium(III)-catalysed cascade [3 + 2] annulation of: N -aryloxyacetamides with 3-(hetero)arylpropiolic acids: Synthesis of benzofuran-2(3 H)-ones
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Herein, a cascade [3 + 2] annulation of N-aryloxyacetamides with 3-(hetero)arylpropiolic acids affording benzofuran-2(3H)-ones via rhodium(iii)-catalyzed redox-neutral C-H functionalization/isomerization/lactonization using an internal oxidative directing group O-NHAc was achieved. This catalytic system provides a regio- and stereoselective approach to synthesize (Z)-3-(amino(aryl)methylene)benzofuran-2(3H)-ones with exclusive Z configuration selectivity, acceptable yields and good functional group tolerance. Preliminary investigations on ultraviolet-visible and fluorescence behaviors reveal that the annulation products may be applied as a promising fluorescent probe for sensing metal cations, especially for cerium (Ce3+).
- Pan, Jin-Long,Liu, Tuan-Qing,Chen, Chao,Li, Quan-Zhe,Jiang, Wei,Ding, Tong-Mei,Yan, Zhi-Qiang,Zhu, Guo-Dong
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supporting information
p. 8589 - 8600
(2019/10/02)
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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 0119; 0120; 0121
(2018/10/19)
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- Sequential protocol for C(sp)–H carboxylation with CO2: KOtBu-catalyzed C(sp)–H silylation and KOtBu-mediated carboxylation
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CO2 incorporation into C–H bonds is an important and interesting topic. Herein a sequential protocol for C(sp)–H carboxylation by employing a metal-free C–H activation/catalytic silylation reaction in conjunction with KOtBu-mediated carboxylation with CO2 was established, in which KOtBu catalyzes silylation of terminal alkynes to form alkynylsilanes at low temperature, and simultaneously mediates carboxylation of the alkynesilanes with atmospheric CO2. Importantly, the carboxylation further promotes the silylation, which makes the whole reaction proceed very rapidly. Moreover, this methodology is simple and scalable, which is characterized by short reaction time, wide substrate scope, excellent functional-group tolerance and mild reaction conditions, affording a range of corresponding propiolic acid products in excellent yields in most cases. In addition, it also allows for a convenient 13C-labeling through the use of 13CO2.
- Yu, Bo,Yang, Peng,Gao, Xiang,Yang, Zhenzhen,Zhao, Yanfei,Zhang, Hongye,Liu, Zhimin
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p. 449 - 456
(2018/02/06)
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- Copper-Catalyzed Decarboxylative/Click Cascade Reaction: Regioselective Assembly of 5-Selenotriazole Anticancer Agents
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A simple and efficient Cu-catalyzed decarboxylative/click reaction for the preparation of 1,4-disubstituted 5-arylselanyl-1,2,3-triazoles from propiolic acids, diselenides, and azides has been developed. The mechanistic study revealed that the intermolecular AAC reaction of an alkynyl selenium intermediate occurred. The resulting multisubstituted 5-seleno-1,2,3-triazoles were tested for in vitro anticancer activity by MTT assay, and compounds 4f, 4h, and 4p showed potent cancer cell-growth inhibition activities.
- Cui, Fei-Hu,Chen, Jing,Mo, Zu-Yu,Su, Shi-Xia,Chen, Yan-Yan,Ma, Xian-Li,Tang, Hai-Tao,Wang, Heng-Shan,Pan, Ying-Ming,Xu, Yan-Li
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supporting information
p. 925 - 929
(2018/02/22)
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- Method for preparing propiolic acid and derivatives thereof under mild condition
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The invention provides a novel method for preparing propiolic acid compounds through a domino reaction. The method comprises a step of subjecting terminal alkyne compounds, hydrosilane and CO2 to thedomino reaction under the catalysis action of Lewis base so as to obtain propiolic acid compounds. According to the invention, common Lewis base is used as a promoter, and corresponding propiolic acidcompounds containing different function groups can be efficiently produced through a reaction of the terminal alkyne compounds with hydrosilane and normal-pressure CO2 under a mild condition (a temperature of 40 DEG D). According to the method, CO2 is used as a raw material; the cheap Lewis base is used as the promoter; usage of precious metals is avoided; the domino reaction is employed; purification and separation of intermediates are not needed; and reaction conditions are mild. Thus, the method is an efficient cheap green synthetic method and has good industrial application value.
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Paragraph 0027; 0028; 0095; 0096
(2018/09/08)
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- CsF-promoted carboxylation of aryl(hetaryl) terminal alkynes with atmospheric CO2 at room temperature
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A CsF-promoted carboxylation of aryl(hetaryl) terminal alkynes with atmospheric CO2 in the presence of trimethylsilylacetylene was developed to give functionalized propiolic acid products at room temperature. A wide range of propiolic acids bearing functional groups was successfully obtained in good to excellent yields. Mechanistic studies demonstrate that in the carboxylation process the alkynylsilane intermediate was first in situ generated, which was then trapped by CO2, giving rise to the corresponding functionalized propiolic acids after acidification. The advantages of this approach include avoiding use of transition-metal catalysts, wide substrate scope together with excellent functional group tolerance, ambient conditions and a facile work-up procedure.
- Yu,Yang,Gao,Yang,Zhao,Zhang,Liu
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supporting information
p. 9250 - 9255
(2017/08/29)
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- Preparation method of propiolic acid compounds
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The invention relates to CO2 activation and conversion and related chemical technical fields, and specifically relates to a synthesis method of propiolic acid compounds. The method is characterized in that in the presence of an added additive and alkalis, terminal alkynes directly react with CO2 to generate propiolic acid compounds. The proper terminal alkyne substrate may be phenyl acetylene, substituted phenyl acetylene, heterocyclic aryl alkynes, or aliphatic terminal alkynes. Compared with the prior art, the invention mainly provides a novel and simple reaction system. According to the preparation method, potassium carbonate is taken as the alkali, quaternary ammonium salts are taken as the additive, and acetonitrile, which is convenient for the post treatment, is taken as the solvent. The preparation method is reported for the first time. The reaction system does not need any transition metal catalyst; the experiment operation is simple; the raw materials are cheap and easily available, and the preparation method is environment-friendly and generates great application value, social benefits, and economic benefits.
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Paragraph 0055-0057
(2017/10/12)
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- Carboxylation of Terminal Alkynes with Carbon Dioxide Catalyzed by an In Situ Ag2O/N-Heterocyclic Carbene Precursor System
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A carboxylation of terminal alkynes with carbon dioxide (CO2) at ambient conditions was developed in situ using a series of N-heterocyclic carbene (NHC) precursors and Ag2O. The unique structure of NHCs largely increases the solubility of active Ag species and meanwhile activates CO2 by forming the NHC–CO2 adduct. This novel catalytic system demonstrated quite low Ag loading, very high activities, wide substrate generality and excellent tolerance for a variety of functionalities. In addition, avoiding cumbersome synthesis procedures, processing, and reserving of the photosensitive Ag complex, this system could be stored and operated as straightforward as the inorganic Ag salt catalysts.
- Yuan, Ye,Chen, Cheng,Zeng, Cheng,Mousavi, Bibimaryam,Chaemchuen, Somboon,Verpoort, Francis
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p. 882 - 887
(2017/03/13)
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- Method for preparing propiolic acid compounds
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The invention discloses a method for preparing propiolic acid compounds. An ionic type iron (III) complex containing monoimide functionalized imidazolium cations is taken as the single-component catalyst, carbon dioxide is taken as the carboxylation reagent, and various propiolic acid compounds are prepared through carboxylation reaction of terminal alkyne under normal pressure. The terminal alkyne substrate relates to phenylacetylene, substituted phenylacetylene, heterocyclic aryne, aromatic diyne or aliphatic series terminal alkyne. The method for preparing the propiolic acid compounds through carboxylation reaction of terminal alkyne and carbon dioxide under the catalysis of the iron-based catalyst is provided for the first time. Compared with the prior art, the method has the advantages that the catalyst is more environmentally friendly, synthesis is easier, reaction conditions are mild, and catalytic activity and functional group tolerance are unchanged or improved.
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Paragraph 0050; 0051
(2016/10/10)
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- Carboxylation of terminal alkynes with CO2 using novel silver N-heterocyclic carbene complexes
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Four novel N-heterocyclic carbene (NHC) silver complexes, I-IV, have been synthesized and characterized. The single X-ray crystal diffraction data indicate a dinuclear solid-state structure for I and III and a mononuclear structure for II and IV. These complexes have been successfully used as efficient catalysts for the C-H activating carboxylation of terminal alkynes with CO2. A wide range of substrates with various functional groups afforded the corresponding aryl or alkyl substituted propiolic acids in good yields under mild conditions. Moreover, the role of bases and the reaction mechanism is thoroughly discussed.
- Li, Shanshan,Sun, Jing,Zhang, Zhizhi,Xie, Ruixia,Fang, Xiangchen,Zhou, Mingdong
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p. 10577 - 10584
(2016/07/07)
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- β-Ketophosphonate formation via aerobic oxyphosphorylation of alkynes or alkynyl carboxylic acids with H-phosphonates
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A synergistic Cu/Fe-catalyzed aerobic oxyphosphorylation of alkynes or alkynyl carboxylic acids with H-phosphonate is disclosed. The useful β-ketophosphonate products were obtained in good yields under oxygen atmosphere in a novel way. This reaction exhibits a wide substrate scope, and the mechanistic experiments indicate that a radical mechanism forms both C-P and C=O bonds simultaneously. This mechanism contrasts existing aerobic difunctionalization of alkynes.
- Zhou, Mingxin,Chen, Ming,Zhou, Yao,Yang, Kai,Su, Jihu,Du, Jiangfeng,Song, Qiuling
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supporting information
p. 1786 - 1789
(2015/04/14)
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- Ruthenium-catalyzed asymmetric [2 + 2] cycloadditions between chiral acyl camphorsultam-substituted alkynes and bicyclic alkenes
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Ruthenium-catalyzed asymmetric [2 + 2] cycloadditions between chiral acyl camphorsultam-functionalized alkynes and bicyclic alkenes were examined, providing adducts with complete exo stereoselectivity in good overall yield and enantioselectivity (up to 99% and 166:1, respectively), as well as appreciable diastereoselectivity (up to 163:1). The diastereoselectivity showed dependence on the solvent and temperature, as well as on the substitution pattern of the reacting alkyne and bicyclic alkene components. In general, higher diastereoselectivities were observed for reactions conducted in ethereal solvents and at lower temperatures between N-propynoyl camphorsultams and bicyclic alkenes.
- Goodreid, Jordan,Villeneuve, Karine,Carlson, Emily,Tam, William
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p. 10002 - 10012
(2015/02/19)
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- CARBOXYLATION OF TERMINAL ALKYNES
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The present invention describes a process for converting a terminal alkyne into an alkynoic acid. In this process the alkyne is exposed to carbon dioxide in the presence of a copper (I) species, a base and a complexing agent capable of complexing copper (I).
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Page/Page column 17-18; 26
(2011/07/07)
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