1483-67-6Relevant articles and documents
Cis -1,2-Bis(diphenylphosphino)ethylene copper(i) catalyzed C-H activation and carboxylation of terminal alkynes
Trivedi, Manoj,Smreker, Jacob R.,Singh, Gurmeet,Kumar, Abhinav,Rath, Nigam P.
, p. 14145 - 14151 (2017)
The reaction of cis-1,2-bis(diphenylphosphino)ethylene (dppet) with CuX (X = CN, SCN) in 1:1 M molar ratio in DCM-MeOH (50:50 V/V) under refluxing conditions gave two dimeric Cu(i) complexes, viz. [Cu2(μ-CN)2(κ2-P,P-dppet)2] (1) and [Cu2(μ2-SCN)2(κ2-P,P-dppet)2] (2). These complexes have been characterized by elemental analyses, IR, 1H and 31P NMR, and electronic absorption spectroscopies, and ESI-MS. The molecular structure of 2 was confirmed by single crystal X-ray diffraction, which indicated that 2 exists as a centrosymmetric dimer in which the two copper centers are bonded to two dppet ligands and two bridging thiocyanate groups in a μ2-manner. The electrochemical properties of 1 and 2 were studied by cyclic voltammetry. Both the complexes exhibited strong luminescence properties in the solution state at ambient temperature. Both the complexes were found to be efficient catalysts for the conversion of terminal alkynes into propiolic acids with CO2. Owing to their excellent catalytic activity, the reactions proceed at atmospheric pressure and ambient temperature (25 °C). The catalytic products were obtained in excellent yields (90-97%) by using the complex loading of 1 mol%.
A Schiff base-modified silver catalyst for efficient fixation of CO2 as carboxylic acid at ambient pressure
Wu, Zhilian,Sun, Lei,Liu, Qinggang,Yang, Xiaofeng,Ye, Xue,Hu, Yancheng,Huang, Yanqiang
, p. 2080 - 2085 (2017)
The fixation of CO2 as a carboxylic acid is a significant reaction for C-C bond formation in organic synthesis. So far, besides C-H carboxylations using stoichiometric amounts of metals or organometallic reagents, great efforts have been devoted to develop new heterogeneous catalyst, while the catalytic performance of supported metal catalysts is not satisfactory. Herein, a Schiff base-modified silver catalyst was developed for the direct carboxylation of terminal alkynes with CO2, enabling an efficient and green synthesis of valuable alkynyl carboxylic acids. The reaction can smoothly proceed under atmospheric pressure and low temperature (60 °C) conditions. Moreover, a silver-based catalyst, which was prepared by an in situ reduction route, can be easily prepared, recovered, and reused five times without significant loss of activity due to the stability promoted by the Schiff-base on the support surface. In addition, the markedly negative influence of H2O and solvent effect on this reaction system has also been discussed.
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
Wang, Wen-Jing,Sun, Zhong-Hua,Chen, Sheng-Chun,Qian, Jun-Feng,He, Ming-Yang,Chen, Qun
, (2021/05/24)
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.
Organocatalytic Strategy for the Fixation of CO2via Carboxylation of Terminal Alkynes
Shi, Jun-Bin,Bu, Qingqing,Liu, Bin-Yuan,Dai, Bin,Liu, Ning
, p. 1850 - 1860 (2021/01/14)
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.
Method for rapidly preparing acetylenic acid and derivatives thereof based on microchannel continuous flow technology
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Paragraph 0027, (2021/05/19)
The invention discloses a method for rapidly preparing acetylenic acid and derivatives thereof based on a microchannel continuous flow technology. The method comprises a lithium-hydrogen exchange reaction and a nucleophilic addition reaction. The lithium-hydrogen exchange reaction comprises the following steps: pumping a terminal alkyne solution and a butyl lithium solution into a first-section microchannel reactor according to a certain equivalent proportion, and carrying out the lithium-hydrogen exchange reaction at a certain temperature for a certain time to generate terminal alkynyl lithium. The nucleophilic addition reaction comprises the following steps: introducing the terminal alkynyl lithium obtained in the lithium hydrogen exchange reaction into a second-section micro-channel reactor, mixing the terminal alkynyl lithium with CO2 gas with a certain equivalent proportion, carrying out reacting for a certain period of time at a certain temperature to generate terminal alkynyl carboxylic acid lithium salt, and acidifying the product to obtain a terminal alkynyl carboxylic acid product. The synthesis method provided by the invention is friendly to environment, high in efficiency, low in cost, mild in conditions and good in substrate universality in virtue of a coupling micro-channel continuous flow technology. According to the invention, the danger coefficient of the lithium-containing reagent is greatly reduced, so the reactions can achieve higher product purity under a controllable continuous condition.
Fixation of CO2 as a carboxylic acid precursor by microcrystalline cellulose (MCC) supported Ag NPs: A more efficient, sustainable, biodegradable and eco-friendly catalyst
Shah, Dharmesh J.,Sharma, Anuj S.,Shah, Akshara P.,Sharma, Vinay S.,Athar, Mohd,Soni, Jigar Y.
supporting information, p. 8669 - 8676 (2019/06/14)
Silver nanoparticles supported on microcrystalline cellulose (Ag NPs@MCC), an active catalyst, has been discovered for the direct carbonylation of terminal alkynes with CO2 into carboxylic acid under mild and sustainable reaction conditions. The stabilized Ag NPs show higher distribution with a uniform particle size. The catalyst was characterized by PXRD, SEM, TEM, HR-TEM, EDS, EDX, ICP-AES and XPS analysis. The Ag NPs@MCC material was found to be more efficient, shows excellent dispersion in various solvents and is biodegradable. The solvent effects on carbonylation of terminal alkynes were well studied both experimentally and computationally. Furthermore, the present catalyst can be recycled in up to five catalytic cycles without significant loss of its activity and is also applicable for the gram scale carbonylation of terminal alkynes.
Structural Elucidation of Trace Components Combining GC/MS, GC/IR, DFT-Calculation and Synthesis—Salinilactones, Unprecedented Bicyclic Lactones from Salinispora Bacteria
Schlawis, Christian,Kern, Simone,Kudo, Yuta,Grunenberg, J?rg,Moore, Bradley S.,Schulz, Stefan
supporting information, p. 14921 - 14925 (2018/10/24)
The analysis of volatiles released by marine Salinispora bacteria uncovered a new class of natural compounds displaying an unusual bicyclic [3.1.0]-lactone skeleton. Although only sub-μg quantities of the compounds were available, the combination of analytical methods, computational spectroscopy, and synthesis allowed unambiguous structural identification of the compounds, called salinilactones, without the need for isolation. Orthogonal hyphenated methods, GC/MS and solid-phase GC/IR allowed to propose a small set of structures consistent with the data. A candidate structure was selected by comparison of DFT-calculated IR spectra and the experimental IR-spectrum. Synthesis confirmed the structure and absolute configuration of three bicyclic lactones, salinilactones A–C. The salinilactones are structurally closely related to the A-factor class of compounds, autoregulators from streptomycete bacteria. They exhibited inhibitory activity against Salinispora and Streptomyces strains.
Copper-Catalyzed Decarboxylative/Click Cascade Reaction: Regioselective Assembly of 5-Selenotriazole Anticancer Agents
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
supporting information, p. 925 - 929 (2018/02/22)
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.
Development of Gold-catalyzed [4+1] and [2+2+1]/[4+2] Annulations between Propiolate Derivatives and Isoxazoles
Sahani, Rajkumar Lalji,Liu, Rai-Shung
supporting information, p. 1026 - 1030 (2017/01/18)
Two new gold-catalyzed annulations of isoxazoles with propiolates have been developed. Most isoxazoles follow an initial O attack on the alkyne to afford a [4+1] annulation product. This process results in a remarkable alkyne cleavage of initial propiolates. Unsubstituted isoxazoles proceed through an N attack step to yield formal [2+2+1]/[4+2] annulation products. These two annulation products arise initially from two seven-membered heterocyclic intermediates, which then lead to products.
Carboxylation of Terminal Alkynes with Carbon Dioxide Catalyzed by an In Situ Ag2O/N-Heterocyclic Carbene Precursor System
Yuan, Ye,Chen, Cheng,Zeng, Cheng,Mousavi, Bibimaryam,Chaemchuen, Somboon,Verpoort, Francis
, p. 882 - 887 (2017/03/13)
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.
