- Core-shell metal-organic frameworks and metal functionalization to access highest efficiency in catalytic carboxylation
-
A core-shell metal-organic frameworks (MOF@MOF) based on the Zr-MOFs assembly from core-structure UiO-66 combined with shell-structure UiO-67-BPY were explored. The synthesized materials were characterized via XRD, FTIR, SEM, TEM, and surface area analysis, etc. indicating the presence of a core-shell structure of UiO-66@UiO-67-BPY. Furthermore, incorporation of the bipyridinic (BPY) group in the linker used to construct the shell layer (UiO-67-BPY) could coordinate with active metal species and thus create an advantage for site-selective metal incorporation in the core-shell structure. Silver (Ag) was selected for the selective metal incorporation and an excellent Ag-dispersion via coordination with the bipyridinic groups in the UiO-67-BPY layer of the core-shell material was obtained. The synthesized material (UiO-66@UiO-67-BPY-Ag) was successfully applied as a heterogeneous catalyst for the CO2 fixation via carboxylation of terminal alkynes. The catalytic material showed excellent yields using at a low Ag-loading under mild reaction condition (50 °C, 1 bar). Moreover, the catalyst can be recycled for at least 5 times maintaining a stable catalytic performance. Interestingly, the high catalytic activity of the synthesized material demonstrated clearly the beneficial advantage of the metalated core-shell structure over the reported routes to synthesize silver catalysts such as encapsulated Ag nanoparticles (AgNP@MOF) or Ag-bidentately coordinated on traditional MOFs applying the same reaction model.
- Gong, Yanyan,Yuan, Ye,Chen, Cheng,Zhang, Pan,Wang, Jichao,Zhuiykov, Serge,Chaemchuen, Somboon,Verpoort, Francis
-
-
Read Online
- DBU and copper(I) mediated carboxylation of terminal alkynes using supercritical CO2 as a reactant and solvent
-
An organic solvent free, DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene)-mediated and copper(I)-catalyzed CH activating carboxylation of terminal alkynes in supercritical CO2 (ScCO2) was developed in this work. Terminal alkynes react with ScCO2 in the presence of CuI/DBU and produce the corresponding functionalized propiolic acids in excellent yields. Under the optimized conditions, carbon dioxide can act as both reactant and solvent for the reaction. DBU serves as a ligand of copper catalyst, nucleophile, and base during the reaction. DBU alone can also mediate the direct CH carboxylation in the absence of transit metal catalyst. But the reaction requires a higher reaction temperature and pressure to obtain desired yields.
- Li, Fa-Wang,Suo, Quan-Ling,Hong, Hai-Long,Zhu, Ning,Wang, Ya-Qi,Han, Li-Min
-
-
Read Online
- Gold-catalyzed homo- And cross-annulation of alkynyl carboxylic acids: a facile access to substituted 4-hydroxy 2: H -pyrones and total synthesis of pseudopyronine A
-
A Au(i)-catalyzed homo- and cross-annulation reaction of alkynyl carboxylic acids offering 3,6-disubstituted 4-hydroxy 2H-pyrones has been demonstrated. The reaction tolerates various substituted alkynyl carboxylic acids and moderate to good yields of α-pyrone scaffolds have been observed. Later, a gram-scale reaction of the acid and the total synthesis of the natural product pseudopyronine A have been carried out successfully.
- Choudhary, Shivani,Gayyur,Ghosh, Nayan,Saxena, Anchal
-
p. 8716 - 8723
(2020/11/17)
-
- Sodium Methyl Carbonate as an Effective C1 Synthon. Synthesis of Carboxylic Acids, Benzophenones, and Unsymmetrical Ketones
-
Reported is the synthesis of carboxylic acids, symmetrical ketones, and unsymmetrical ketones with selectivity achieved by exploiting the differential reactivity of sodium methyl carbonate with Grignard and organolithium reagents.
- Hurst, Timothy E.,Deichert, Julie A.,Kapeniak, Lucas,Lee, Roland,Harris, Jesse,Jessop, Philip G.,Snieckus, Victor
-
supporting information
p. 3882 - 3885
(2019/06/07)
-
- Copper-Catalyzed Decarboxylative/Click Cascade Reaction: Regioselective Assembly of 5-Selenotriazole Anticancer Agents
-
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
-
supporting information
p. 925 - 929
(2018/02/22)
-
- Cobalt(III)-Catalyzed Construction of Benzofurans, Benzofuranones and One-Pot Orthogonal C?H Functionalizations to Access Polysubstituted Benzofurans
-
Benzofuran and benzofuranone derivatives have been synthesized through exclusive 5-exo-dig intramolecular hydroarylation using the amide-directed, cost-effective, high-valent Cp*CoIII-catalytic system. Challenging one-pot, orthogonal C?H functionalizations using two different electrophiles are also reported to afford polysubstituted benzofurans. Several valuable functional group interconversions along with removal of the amide directing group provide a route to access several diversely functionalized benzofurans. The mechanistic study suggests a reversible cobaltation step is operative here. (Figure presented.).
- Bera, Sourav Sekhar,Debbarma, Suvankar,Jana, Sripati,Maji, Modhu Sudan
-
supporting information
p. 2204 - 2210
(2018/06/07)
-
- Carboxylation of Terminal Alkynes with Carbon Dioxide Catalyzed by an In Situ Ag2O/N-Heterocyclic Carbene Precursor System
-
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
-
p. 882 - 887
(2017/03/13)
-
- Carboxylation of terminal alkynes with CO2 using novel silver N-heterocyclic carbene complexes
-
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
-
p. 10577 - 10584
(2016/07/07)
-
- Copper-Catalyzed Domino Synthesis of Benzo[4,5]imidazo[1,2-a]pyrimidin-4(10H)-ones using Cyanamide as a Building Block
-
An efficient and practical copper-catalyzed domino synthesis of benzo[4,5]imidazo[1,2-a]pyrimidin-4(10H)-ones has been developed. The protocol uses N-(2-halophenyl)-3-alkylpropiolamides and cyanamide as the starting materials, inexpensive copper(I) iodide and pipecolinic acid as the catalyst and ligand, and the corresponding products were obtained in moderate to good yields.
- Lou, Zhenbang,Wu, Xudong,Yang, Haijun,Zhu, Changjin,Fu, Hua
-
supporting information
p. 3961 - 3968
(2016/01/25)
-
- PROCESS FOR PREPARING A PROPIOLIC ACID OR A DERIVATIVE THEREOF
-
The invention relates to a process for preparing a propiolic acid or a derivative thereof by reacting a terminal alkyne with carbon dioxide, which comprises performing the reaction in the presence of a base and a copper complex, especially a copper (I) complex having at least one ligand, at least one of the ligands of the copper complex being selected from monodentate ligands which have an aminic or iminic nitrogen atom capable of coordination with copper, and polydentate ligands having at least two atoms or atom groups which are capable of simultaneous coordination with copper and are selected from nitrogen, oxygen, sulfur, phosphorus and carbene carbon.
- -
-
Paragraph 0126
(2014/02/15)
-
- A palladium nanoparticle-nanomicelle combination for the stereo-selective semihydrogenation of alkynes in water at room temperature
-
The addition of NaBH4 to Pd(OAc) 2 in water containing nanomicelles leads to the generation of H2 and Pd nanoparticles. Subsequent reduction of disubstituted alkynes affords Z-alkenes in high yields. These reactions are general, take place in water at ambient temperatures, and offer recycling of the aqueous reaction mixture along with low overall E Factors.
- Slack, Eric D.,Gabriel, Christopher M.,Lipshutz, Bruce H.
-
supporting information
p. 14051 - 14054
(2015/02/19)
-
- Stereoselective silylcupration of conjugated alkynes in water at room temperature
-
Micellar catalysis enables copper-catalyzed silylcupration of a variety of electron-deficient alkynes, thereby providing access to isomerically pure E- or Z-β-silyl-substituted carbonyl derivatives. These reactions take place in minutes, afford high yields and stereoselectivity, and are especially tolerant of functional groups present in the substrates. The aqueous reaction medium has been successfully recycled several times, and a substrate/catalyst ratio of 10,000:1 has been documented for this methodology. Fast, cheap, and green: Micellar catalysis enables the selective construction of a variety β-silyl-substituted carbonyl derivatives under mild aqueous conditions. The reaction is catalyzed by low levels of CuI, is compatible with numerous electron-withdrawing groups, affords high yields, and provides opportunities for scale-up and recycling of the reaction medium. The environmental impact, as measured by E Factors, is very low.
- Linstadt, Roscoe T. H.,Peterson, Carl A.,Lippincott, Daniel J.,Jette, Carina I.,Lipshutz, Bruce H.
-
supporting information
p. 4159 - 4163
(2014/05/06)
-
- Ruthenium-catalyzed asymmetric [2 + 2] cycloadditions between chiral acyl camphorsultam-substituted alkynes and bicyclic alkenes
-
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
-
p. 10002 - 10012
(2015/02/19)
-
- Carboxylation of alkynylsilanes with carbon dioxide mediated by cesium fluoride in DMSO
-
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
-
supporting information
p. 3773 - 3775
(2014/03/21)
-
- Ligand-free Ag(I)-catalyzed carboxylation of terminal alkynes with CO 2
-
Chemical equations presented. A convenient approach to selectively prepare a wide range of functionalized propiolic acids was developed by AgI-catalyzed carboxylation of terminal alkynes using carbon dioxide as carboxylative agent under ligand-free conditions.
- Zhang, Xiao,Zhang, Wen-Zhen,Ren, Xiang,Zhang, Lin-Lin,Lu, Xiao-Bing
-
supporting information; experimental part
p. 2402 - 2405
(2011/06/25)
-
- Synthesis of propiolic acids via copper-catalyzed insertion of carbon dioxide into the C-H bond of terminal alkynes
-
A highly effective copper catalyst has been developed that promotes the insertion of carbon dioxide into the C-H bond of terminal alkynes under unprecedentedly mild conditions. For the first time, propiolic acids can thus be synthesized in excellent yields from alkynes and carbon dioxide in the presence of the mild base cesium carbonate. The catalyst, (4,7-diphenyl-1,10- phenanthroline)bis[tris(4-fluorophenyl)phosphine]copper(I) nitrate, is easy accessible and relatively stable against air and water. Copyright
- Goossen, Lukas J.,Rodriguez, Nuria,Manjolinho, Filipe,Lange, Paul P.
-
supporting information; experimental part
p. 2913 - 2917
(2011/02/22)
-
- Deuteration of α,β-acetylenic esters, amides, or carboxylic acids without using deuterium gas: Synthesis of 2,2,3,3-tetradeuterioesters, amides, or acids
-
An easy, simple, rapid, and nonhazardous deuteration of the C-C triple bond of α,β-acetylenic esters, amides, or acids by means of samarium diiodide in the presence of D2O, provides an efficient method for synthesizing 2,2,3,3-tetradeuterioesters, amides, or carboxylic acids, respectively. When H2O is used instead of D2O, saturated carboxylic esters, amides, or acids were isolated. A mechanism to explain these reduction reactions has been proposed.
- Concellón, José M.,Rodríguez-Solla, Humberto,Concellón, Carmen
-
p. 2129 - 2131
(2007/10/03)
-
- Electrochemical selective incorporation of CO2 into terminal alkynes and diynes
-
Electrochemical incorporation of CO2 into terminal alkynes and diynes on silver cathodes occurred selectively, to afford monocarboxylic acid derivatives in good yields. The electrolyses were carried out in one-compartment cells fitted with magnesium anodes, under mild conditions.
- Ko?ster, Frank,Dinjus, Erkhardt,Din?ach, Elisabet
-
p. 2507 - 2511
(2007/10/03)
-
- Synthesis of 2-acetylenic carboxylic acids, 1-sulfinyl and 1-sulfonyl- 2-ketones from 2-acetylenic phenyl sulfides
-
Monochlorination at the 1-position with sulfuryl chloride, followed by methanolysis converted 2-acetylenic phenyl sulfides into 1-methoxy-2- acetylenic phenyl sulfides. Oxidation with chromic acid gave 2-acetylenic carboxylic acids. Oxidation of 2-acetylenic phenyl sulfides with Oxone and hydrogen peroxide in acetic acid gave the corresponding sulfoxides and sulfones respectively. Diethylamine addition to the triple bond produced enamines which were hydrolyzed with aqueous hydrochloric acid to the corresponding 1-sulfinyl and 1-sulfonyl-2-ketones.
- Fortes, Carlos C.,Garrote, Clevia F.D.
-
p. 2993 - 3026
(2007/10/03)
-
- Ligand-directed reaction products in the nickel-catalyzed electrochemical carboxylation of terminal alkynes
-
The influence of a series of N and P ligands in the nickel-catalyzed electrochemical carboxylation of 1-octyne has been studied.Different carboxylic acids are obtained depending on the nature of the ancillary ligand, and results afford an example of high ligand-directed product specificity.
- Labbe, Eric,Dunach, Elisabet,Perichon, Jacques
-
p. C51 - C56
(2007/10/02)
-
- Chain-extension Reactions of Acetylenes. Part 4. Reaction of 1,3-Dilithioacetylides with Carbonyl Electrophiles, Hexamethylphosphoric Triamide, and Benzylideneaniline
-
The regioselectivity of the reactions of 1,3-dilithioalk-1-ynes with various electrophiles has been examined.With formaldehyde and cyclic ketones, reaction occur at C-1 and C-3 to give alk-2-yne-1,5-diols.In contrast reactions with carbon dioxide give allene-1,3-dicarboxylic acids. 1,3-Dilithioalk-1-ynes decompose hexamethylphosphoric triamide and the resulting N-methylmethyleneamine undergoes addition only at the propargylic site.Further reaction with either 1-bromobutane or water gives alkynylamines.Benzylideneaniline also reacts with 1,3-dilithiohex- and hept-1-ynes only at the propargylic site to give N-phenylbut-3-ynylamines.
- Pover, Keith A.,Scheinmann, Feodor
-
p. 2338 - 2345
(2007/10/02)
-