133645-41-7Relevant articles and documents
A green and recyclable CuSO4·5H2O/ionic liquid catalytic system for the CO2-promoted hydration of propargyl alcohols: an efficient assembly of α-hydroxy ketones
Yuan, Ye,Hu, Jia,Wang, Yu,Huang, Leilei,Zheng, Jiayun,Zhao, Yufeng,Chen, Yiyun,Chen, Cheng,Verpoort, Francis
, p. 561 - 570 (2021/12/03)
α-Hydroxy ketones are important building blocks in biological, pharmaceutical and synthetic chemistry. In this work, diverse α-hydroxy ketones were efficiently constructed through the CO2-promoted hydration process of propargyl alcohols, which was catalyzed by a system consisted of economical CuSO4·5H2O and a green 1-butyl-3-methylimidazolium acetate ionic liquid. Particularly, this catalytic system exhibited excellent activity under atmospheric CO2 or even mimetic flue gas (20 vol% of CO2). Moreover, this system employed the lowest metal loading ever reported (0.004–0.25 mol%) meanwhile reached the highest turnover number (11700) for the target hydration reaction. Additionally, this is the first reported Cu catalytic system with reliable recyclability, which could be easily reused at least 6 times with yields higher than 85%.
Synthesis of Α-hydroxy ketones by copper(I)-catalyzed hydration of propargylic alcohols: CO2 as a cocatalyst under atmospheric pressure
Zhou, Zhi-Hua,Zhang, Xiao,Huang, Yong-Fu,Chen, Kai-Hong,He, Liang-Nian
, p. 1345 - 1351 (2019/08/07)
Inexpensive and efficient Cu(I) catalysis is reported for the synthesis of α-hydroxy ketones from propargylic alcohols, CO2, and water via tandem carboxylative cyclization and nucleophilic addition reaction. Notably, hydration of propargylic alcohols can be carried out smoothly under atmospheric CO2 pressure, generating a series of α-hydroxy ketones efficiently and selectively. This strategy shows great potential for the preparation of valuable α-hydroxy ketones by using CO2 as a crucial cocatalyst under mild conditions.
AgI/TMG-Promoted Cascade Reaction of Propargyl Alcohols, Carbon Dioxide, and 2-Aminoethanols to 2-Oxazolidinones
Li, Xue-Dong,Song, Qing-Wen,Lang, Xian-Dong,Chang, Yao,He, Liang-Nian
, p. 3182 - 3188 (2017/10/03)
Chemical valorization of CO2 to access various value-added compounds has been a long-term and challenging objective from the viewpoint of sustainable chemistry. Herein, a one-pot three-component reaction of terminal propargyl alcohols, CO2, and 2-aminoethanols was developed for the synthesis of 2-oxazolidinones and an equal amount of α-hydroxyl ketones promoted by Ag2O/TMG (1,1,3,3-tetramethylguanidine) with a TON (turnover number) of up to 1260. By addition of terminal propargyl alcohol, the thermodynamic disadvantage of the conventional 2-aminoethanol/CO2 coupling was ameliorated. Mechanistic investigations including control experiments, DFT calculation, kinetic and NMR studies suggest that the reaction proceeds through a cascade pathway and TMG could activate propargyl alcohol and 2-aminoethanol through the formation of hydrogen bonds and also activate CO2.
Thermodynamically favorable synthesis of 2-oxazolidinones through silver-catalyzed reaction of propargylic alcohols, CO2, and 2-aminoethanols
Song, Qing-Wen,Zhou, Zhi-Hua,Wang, Mei-Yan,Zhang, Kan,Liu, Ping,Xun, Jia-Yao,He, Liang-Nian
, p. 2054 - 2058 (2017/07/25)
Development of catalytic routes to incorporate CO2 into carbonyl compounds at mild conditions remains attractive and challenging. Herein, a one-pot three-component cascade reaction of terminal propargylic alcohols, CO2, and 2-aminoethanols through AgI-based catalysis is reported for the synthesis of carbonyl compounds through C—O/C—N bond formation. This thermodynamically favorable route can be ingeniously regulated to afford a wide range of 2-oxazolidinones along with concurrent production of α-hydroxyl ketone derivatives in excellent yields and selectivity. Preliminary mechanistic studies indicate that such a process proceeds through successive formation of α-alkylidene cyclic carbonate, β-oxopropylcarbamate, and 2-oxazolidinones.
Task-specific ionic liquid and CO2-cocatalysed efficient hydration of propargylic alcohols to α-hydroxy ketones
Zhao, Yanfei,Yang, Zhenzhen,Yu, Bo,Zhang, Hongye,Xu, Huanjun,Hao, Leiduan,Han, Buxing,Liu, Zhimin
, p. 2297 - 2301 (2015/03/30)
The hydration of propargylic alcohols is a green route to synthesize α-hydroxy ketones. Herein a CO2-reactive ionic liquid (IL), [Bu4P][Im], was found to display high performance for catalyzing the hydration of propargylic alcohols in the presence of atmospheric CO2, and a series of propargylic alcohols could be converted into the corresponding α-hydroxy ketones in good to excellent yields. In the IL/CO2 reaction system, CO2 served as a cocatalyst by forming α-alkylidene cyclic carbonates with propargylic alcohols, and was released via the rapid hydrolysis of the carbonates catalysed by the IL. This is the first example of the efficient hydration of propargylic alcohols under metal-free conditions. This journal is
Efficient synthesis of tertiary α-hydroxy ketones through CO 2-promoted regioselective hydration of propargylic alcohols
He, Haitao,Qi, Chaorong,Hu, Xiaohan,Guan, Yuqi,Jiang, Huanfeng
supporting information, p. 3729 - 3733 (2014/08/05)
A carbon dioxide-promoted and silver acetate-catalyzed hydration of propargylic alcohols for the efficient synthesis of tertiary α-hydroxy ketones has been developed. The reaction is proposed to proceed via a tandem process of carbon dioxide incorporation into propargylic alcohols and subsequent hydrolysis. This journal is the Partner Organisations 2014.
Effective guanidine-catalyzed synthesis of carbonate and carbamate derivatives from propargyl alcohols in supercritical carbon dioxide
Ca', Nicola Della,Gabriele, Bartolo,Ruffolo, Giuseppe,Veltri, Lucia,Zanetta, Tito,Costa, Mirco
supporting information; experimental part, p. 133 - 146 (2011/04/18)
The reactions of propargyl alcohols with carbon dioxide in supercritical carbon dioxide or in acetonitrile with gaseous carbon dioxide in the presence of organic bases as catalysts have been examined. Bicyclic guanidines are effective catalysts for the formation of α-methylene cyclic carbonates under mild reaction conditions. Oxoalkyl carbonates, oxoalkyl carbamates or α-methyleneoxazolidinones are obtained in high yields and good selectivities in one-step starting from propargyl alcohols and an external nucleophile (alcohols or amines) using bicyclic guanidines as catalysts in supercritical carbon dioxide. Propargylic diols under the same reaction conditions underwent a rearrangement process instead of carbon dioxide insertion whereas in the presence of an external nucleophile the formation of oxocarbonates, oxocarbamates or cyclic carbamates was achieved in satisfactory yields.
Analogues of Acifran: Agonists of the high and low affinity niacin receptors, GPR109a and GPR109b
Jung, Jae-Kyu,Johnson, Benjamin R.,Duong, Tracy,Decaire, Marc,Uy, Jane,Gharbaoui, Tawfik,Boatman, P. Douglas,Sage, Carleton R.,Chen, Ruoping,Richman, Jeremy G.,Connolly, Daniel T.,Semple, Graeme
, p. 1445 - 1448 (2007/10/03)
Recently identified GPCRs, GPR109a and GPR109b, the high and low affinity receptors for niacin, may represent good targets for the development of HDL elevating drugs for the treatment of atherosclerosis. Acifran, an agonist of both receptors, has been tested in human subjects, yet until recently very few analogs had been reported. We describe a series of acifran analogs prepared using newly developed synthetic pathways and evaluated as agonists for GPR109a and GPR109b, resulting in identification of compounds with improved activity at these receptors.
Asymmetric catalysis, 132 Metal-catalyzed enantioselective α-Ketol rearrangements
Brunner, Henri,Stoehr, Frank
, p. 2777 - 2786 (2007/10/03)
Promoted by catalytic amounts of transition-metal complexes, the tertiary α-hydroxy ketones 1, 3, 5/6 undergo α-ketol rearrangements to afford equilibrium mixtures of isomers with a reorganization of the carbon skeleton. The range of metal complexes catalyzing the isomerizations is large; the best results were obtained with the catalyst systems NiCl2/ TMEDA, Ni(acac)2, and Ni(acac)2/TMEDA (TMEDA = N,N,N',N'-tetramethyl-1,2-diaminoethane). The catalytic rearrangements were performed at 130 °C in the absence of solvent, with a Ni/ligand/substrate ratio of 1:2:100. The equilibrium composition of the model system 1/2 is 12.5:87:5. The conversion of the achiral substrates 1 and 3 into the chiral products 2 and 4 can be used for kinetic resolution. However, the reverse reactions 2 → 1 and 4 → 3 in the equilibrations narrow the window for asymmetric induction with enantioselective catalysts of the metal component/optically active ligand type. In system 1, the highest enantiomeric excess was achieved with the catalyst systems NiCl2/pybox [18.9% (S)-2] and Ni(acac)2/pybox [19.3% (R)-2] {pybox = 2,6-bis[(S)-4-isopropyl(oxazolin-2'-yl)]pyridine}. The α-ketol rearrangement of 3 with the Ni(acac)2/pybox catalyst resulted in a maximum enantiomeric excess of 37.1% (S)-4.
Cobaltocene-Catalyzed Reaction of Carbon Dioxide with Propargyl Alcohols
Inoue, Yoshio,Ishikawa, Jiro,Taniguchi, Masaaki,Hashimoto, Harukichi
, p. 1204 - 1206 (2007/10/02)
The reaction of carbon dioxide with α-ethynyl tertiary alcohols has been catalyzed by cobaltocene to give α-methylene cyclic carbonates in good yields. α-Ethynyl primary or secondary alcohols give noncyclic alkyl carbonates in fair yields.
