7358-93-2Relevant academic research and scientific papers
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; 0030, (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.
Design and Remarkable Efficiency of the Robust Sandwich Cluster Composite Nanocatalysts ZIF-8@Au25@ZIF-67
Yun, Yapei,Sheng, Hongting,Bao, Kang,Xu, Li,Zhang, Yu,Astruc, Didier,Zhu, Manzhou
supporting information, p. 4126 - 4130 (2020/03/05)
Heterogeneous catalysts with precise surface and interface structures are of great interest to decipher the structure-property relationships and maintain remarkable stability while achieving high activity. Here, we report the design and fabrication of the new sandwich composites ZIF-8@Au25@ZIF-67[tkn] and ZIF-8@Au25@ZIF-8[tkn] [tkn = thickness of shell] by coordination-assisted self-assembly with well-defined structures and interfaces. The composites ZIF-8@Au25@ZIF-67 efficiently catalyzed both 4-nitrophenol reduction and terminal alkyne carboxylation with CO2 under ambient conditions with remarkably improved activity and stability, compared to the simple components Au25/ZIF-8 and Au25@ZIF-8, highlighting the highly useful function of the ultrathin shell. In addition, the performances of these composite sandwich catalysts are conveniently regulated by the shell thickness. This concept and achievements should open a new avenue to the targeted design of well-defined nanocatalysts with enhanced activities and stabilities for challenging reactions.
Sodium Methyl Carbonate as an Effective C1 Synthon. Synthesis of Carboxylic Acids, Benzophenones, and Unsymmetrical Ketones
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)
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.
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.
Method for preparing propiolic acid and derivatives thereof under mild condition
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Paragraph 0027; 0028; 0167; 0168, (2018/09/08)
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.
Sequential protocol for C(sp)–H carboxylation with CO2: KOtBu-catalyzed C(sp)–H silylation and KOtBu-mediated carboxylation
Yu, Bo,Yang, Peng,Gao, Xiang,Yang, Zhenzhen,Zhao, Yanfei,Zhang, Hongye,Liu, Zhimin
, p. 449 - 456 (2018/02/06)
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.
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.
Rational encapsulation of atomically precise nanoclusters into metal-organic frameworks by electrostatic attraction for CO2 conversion
Sun, Lili,Yun, Yapei,Sheng, Hongting,Du, Yuanxin,Ding, Yimin,Wu, Pei,Li, Peng,Zhu, Manzhou
supporting information, p. 15371 - 15376 (2018/08/17)
Controlled encapsulation of atomically precise nanoclusters (APNCs) into metal-organic frameworks (MOFs) has been an efficient way to create new types of multifunctional crystalline porous materials. Such hybrids (APNCs@MOFs) provide ideal candidates for studying inherent structure-catalysis relationships owing to the well-defined compositions of both components. Moreover, modeling of APNCs@MOFs with precise structures would be more reliable. Herein, we have established an "Electrostatic Attraction Strategy" to synthesize APNCs@MOF catalysts and studied their performance as catalysts for the conversion of CO2. The synthetic strategy presented here has been proved to be general, as evidenced by the syntheses of various APNCs@MOF catalysts including all the combinations of [Au12Ag32(SR)30]4-, [Ag44(SR)30]4-, and [Ag12Cu28(SR)30]4- nanoclusters with ZIF-8, ZIF-67, and MHCF frameworks. In particular, the as-obtained Au12Ag32(SR)30@ZIF-8 composite shows excellent performance in capturing CO2 and converting phenylacetylene into phenylpropiolate under mild conditions (50 °C and ambient CO2 pressure) with a TON as high as 18164, far exceeding those of most known catalysts. What's more, the catalyst is very stable and reused 5 times without loss of catalytic activity. We anticipate that this general synthetic approach may open up a new frontier in the development of promising APNCs@MOF catalysts, which can be applied in a broad range of heterogeneous catalyses in the future.
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.
