590-93-2Relevant academic research and scientific papers
Thermal Stability of 2-Butynoic Acid (Tetrolic Acid)
Ashton, Hannah,Bethel, Paul A.,Cantlie, Sarah-Kate,Churchill, Trevor,Cooper, Katie,Dobson, Benjamin,Golden, Michael,Hoyle, Mark
, p. 1101 - 1104 (2019)
Work to assess the thermal properties of 2-butynoic acid (a precursor to acalabrutinib) has revealed the potential for thermal runaway on heating; testing using accelerated rate calorimetry (ARC) showed exothermic onset from 135 °C, precluding short-path distillation as a means of purification. Recrystallization was shown to be effective as an alternative technique to purify the compound and avoid the distillation procedure.
Access to Triazolopiperidine Derivatives via Copper(I)-Catalyzed [3+2] Cycloaddition/Alkenyl C?N Coupling Tandem Reactions
Xiao, Guorong,Wu, Kaifu,Zhou, Wei,Cai, Qian
supporting information, p. 4988 - 4991 (2021/10/14)
A copper-catalyzed [3+2] cylcoaddition/ alkenyl C?N coupling tandem reaction was demonstrated. It provided a method for the formation of triazolopiperidine skeletons. (Figure presented.).
Metal-Organic Framework Based on Heptanuclear Cu-O Clusters and Its Application as a Recyclable Photocatalyst for Stepwise Selective Catalysis
Zhou, Jie,Huang-Fu, Xu,Huang, Yang-Ying,Cao, Chu-Ning,Han, Jie,Zhao, Xiao-Li,Chen, Xu-Dong
, p. 254 - 263 (2019/12/04)
Visible-light driven photoreactions using metal-organic frameworks (MOFs) as catalysts are promising with regard to their environmental friendly features such as the use of renewable and sustainable energy of visible light and potential catalyst recyclability. To develop potential heterogeneous photocatalysts, a family of three copper(II) coordination polymers bearing different Cu-O assemblies have been synthesized with the ligand 4,4-disulfo-[1,1-biphenyl]-2,2-dicarboxylate acid (H4DSDC), namely, {[Cu7(DSDC)2(OH)6(H2O)10]·xH2O}n (1), {[Cu4(DSDC)(4,4-bpy)2(OH)4]·2H2O}n (2), and {Cu2(DSDC)(phen)2(H2O)2}n (3) (4,4-bpy = 4,4-bipyridine and phen = 1,10-phenanthroline). Complex 1 represents a metal-organic framework featuring a NbO type topology constructed from the infinite linkage of heptanuclear [Cu7(μ3-OH)6(H2O)10]8+ clusters by deprotonated DSDC4- ligands, comprising one-dimensional hexagonal channels of a diameter around 11 ? that are filled with water molecules. The infinite waving {[Cu2(OH)2]2+}n ladderlike chains in complex 2 are bridged by DSDC4- and 4,4-bpy ligands into a three-dimensional framework. A two-dimensional layered structure is formed in complex 3 due to the existence of terminal phenanthroline ligands. All of the coordination polymers 1-3 are able to catalyze the visible-light driven oxidation of alcohols at mild conditions using hydrogen peroxide as an oxidant, in which complex 1 demonstrates satisfactory efficiency. Significantly for this photoreaction catalyzed by 1, the extent of oxidation over aryl primary alcohols is fully controllable with time-resolved product selectivity, giving either corresponding aldehydes or carboxylate acids in good yields. It is also remarkable that the photocatalyst could be recovered almost quantitatively on completion of the catalytic cycle without any structure change, and could be recycled for catalytic use for at least five cycles with constant efficiency. This photocatalyst with time-resolved selectivity for different products may provide new insight into the design and development of novel catalytic systems.
Preparation method of 2-butynoic acid
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Paragraph 0050-0063, (2020/01/25)
The invention relates to the technical field of preparation of 2-butynoic acid, in particular to a preparation method of 2-butynoic acid. The preparation method provided by the invention comprises thefollowing steps: mixing 2-butyn-1-ol, a catalyst, hypochlorite, an alkaline substance and water, carrying out an oxidation reaction, and adding an acid to obtain the 2-butyne acid. On the basis of not using a phase transfer catalyst, high yield and purity of 2-butynoic acid are ensured. According to the embodiment, the high performance liquid chromatography (HPLC) purity of the 2-butynoic acid prepared by the preparation method is more than or equal to 99.6%, and the yield is more than or equal to 52.7%.
Rh-Catalyzed Asymmetric Hydrogenation of Unsaturated Medium-Ring NH Lactams: Highly Enantioselective Synthesis of N-Unprotected 2,3-Dihydro-1,5-benzothiazepinones
Yin, Congcong,Yang, Tao,Pan, Yingmin,Wen, Jialin,Zhang, Xumu
supporting information, p. 920 - 923 (2020/02/04)
A straightforward method to prepare 1,5-benzothiazepines was reported. Catalyzed by a Rh/Zhaophos complex, unsaturated cyclic NH lactams with a medium-size ring were hydrogenated smoothly, giving remarkably high enantioselectivities. The sulfur atom in the substrates did not bring an inhibition which was observed with commercially available bisphosphine ligands. This method was successfully applied in the scale-up synthesis of (R)-(-)-thiazesim.
Asymmetric total synthesis of naturally occurring spirocyclic tetranorsesquiterpenoid lanceolactone A
Acharyya, Ranjan Kumar,Nanda, Samik
, p. 5027 - 5035 (2018/07/25)
Asymmetric total synthesis of naturally occurring γ-butenolide containing [4.4]spiro-tetrahydrofuran lanceolactone A has been reported in the present work. Bimetallic ("Pd-Cu") cascade cyclization was the crucial reaction employed for the construction of the γ-butenolide framework of the natural product. Subsequently, iodocyclization and reductive deiodination through a transfer hydrogenation reaction were applied to access the target molecule in an efficient manner.
Carbene-catalyzed LUMO activation of alkyne esters for access to functional pyridines
Mou, Chengli,Wu, Jichang,Huang, Zhijian,Sun, Jun,Jin, Zhichao,Chi, Yonggui Robin
supporting information, p. 13359 - 13362 (2017/12/26)
A carbene-catalyzed LUMO activation of α,β-unsaturated alkyne esters is reported. This catalytic process allows for effective reactions of alkyne esters with enamides to synthesize functional pyridines via simple protocols. A previously unexplored unsaturated alkyne acyl azolium intermediate is involved in the key step of the reaction.
Copper-Catalyzed Domino Synthesis of Benzo[4,5]imidazo[1,2-a]pyrimidin-4(10H)-ones using Cyanamide as a Building Block
Lou, Zhenbang,Wu, Xudong,Yang, Haijun,Zhu, Changjin,Fu, Hua
supporting information, p. 3961 - 3968 (2016/01/25)
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.
Benzannulation of triynes to generate functionalized arenes by spontaneous incorporation of nucleophiles
Karmakar, Rajdip,Yun, Sang Young,Chen, Jiajia,Xia, Yuanzhi,Lee, Daesung
supporting information, p. 6582 - 6586 (2015/06/02)
The thermal reaction of ester-tethered 1,3,8-triynes provides novel benzannulation products with concomitant incorporation of a nucleophile. Evidence suggests that this reaction proceeds via an allene-enyne intermediate generated by an Alder-ene reaction in the first step. Depending on the substituent of the alkyne moiety on the allene-enyne intermediate, the subsequent transformation can take one of two different paths, each leading to discrete aromatization products. The benzannulation of a silane-substituted 1,3,8-triynes provides arene products with a nucleophile incorporated onto the newly formed benzene core, whereas an aryl substituent leads to nucleophile trapping at the benzylic carbon atom connected to the aryl substituent. The formation of these two different products results from the involvement of two regioisomeric allene-enyne intermediates.
Palladium-catalyzed oxidative aminocarbonylation by decarboxylative coupling: Synthesis of alkynyl amides
Hwang, Jinil,Choi, Jinseop,Park, Kyungho,Kim, Wonyoung,Song, Kwang Ho,Lee, Sunwoo
, p. 2235 - 2243 (2015/04/14)
Alkynyl amides were synthesized from a palladium-catalyzed coupling reaction of alkynyl carboxylic acids and amines under carbon monoxide. The reaction was conducted with palladium(II) acetate (5 mol-%) and silver(I) oxide (1.0 equiv.) in acetonitrile at 80 °C for 1 h. This method provides good to moderate product yields and good functional group tolerance towards ketone, ester, and nitrile groups.
