40032-57-3Relevant academic research and scientific papers
Ag-Catalyzed or Ag/PPh3-Catalyzed Chemoselective Switchable Cascade Reactions of N-Propargyl Thiocarbamoyl Fluorides and Malonate Esters
Cai, Zhongliang,Zhou, Junyi,Yu, Miao,Jiang, Liqin
supporting information, p. 293 - 298 (2022/01/12)
The divergent chemoselective synthesis of 2-methylene-2,3-dihydrothiazoles and 4-benzylidene pyrrolidine-2-thiones (most with E stereoselectivity) from N-propargyl thiocarbamoyl fluorides and malonate esters in moderate to excellent yields with a broad substrate scope and functional group tolerance has been accomplished. AgNTf2 catalyst at 60 °C in dichloroethane provided 4-benzylidene pyrrolidine-2-thiones. AgOTf catalyst and PPh3 ligand in refluxing acetonitrile resulted in a complete switch in the reactivity of formed α,α-diester thioamide intermediates followed by isomerization to access 2-methylene-2,3-dihydrothiazoles.
N-Cyanation of Primary and Secondary Amines with Cyanobenzio-doxolone (CBX) Reagent
Chen, Zimin,Yuan, Weiming
supporting information, p. 14836 - 14840 (2021/09/30)
An efficient electrophilic N-cyanation of amines with a stable and less-toxic cyanobenziodoxole reagent towards the synthesis of cyanamides is disclosed. This synthetically practicable strategy allows the construction of a wide variety of cyanamides under very mild and simple conditions with a broad functional group compatibility, and showcases a huge potential in late-stage modification of complex molecules.
One-pot, two-step synthesis of 7-methylene-1,5-piperazine-fused 1,2,3-triazoles
Kuang, Lu,Ming, Peng,Wan, Chang-Feng,Chen, Jun-Min,Sheng, Shou-Ri
, p. 563 - 569 (2020/11/19)
A facile, one-pot two-step synthesis of 7-methylene-1,5-piperazine-fused 1,2,3-triazole derivatives has been developed. The protocol employs an N-allylation of N-propargylated amines with 2,3-dibromopropene in the presence of K2CO3 in DMSO and a CuI-catalyzed [3 + 2] cycloaddition reaction of the synthetic N-(2-bromoallyl)-N-propargyl amines with sodium azide sequentially. Such a method provides methylene-substituted 1,2,3-triazole fused piperazines with some advantages such as simple operation, high efficiency and good product yield (80–91%) through readily available starting materials.
Enantioselective Carboetherification/Hydrogenation for the Synthesis of Amino Alcohols via a Catalytically Formed Chiral Auxiliary
Buzzetti, Luca,Puri??, Mikus,Greenwood, Phillip D. G.,Waser, Jerome
supporting information, p. 17334 - 17339 (2020/11/02)
Chiral auxiliaries and asymmetric catalysis are the workhorses of enantioselective transformations, but they still remain limited in terms of either efficiency or generality. Herein, we present an alternative strategy for controlling the stereoselectivity of chemical reactions. Asymmetric catalysis is used to install a transient chiral auxiliary starting from achiral precursors, which then directs diastereoselective reactions. We apply this strategy to a palladium-catalyzed carboetherification/hydrogenation sequence on propargylic amines, providing fast access to enantioenriched chiral amino alcohols, important building blocks for medicinal chemistry and drug discovery. All stereoisomers of the product could be accessed by the choice of ligand and substituent on the propargylic amine, leading to a stereodivergent process.
Palladium-Catalyzed Carboxy-Alkynylation of Propargylic Amines Using Carbonate Salts as Carbon Dioxide Source
Greenwood, Phillip D. G.,Waser, Jerome
supporting information, p. 5183 - 5186 (2019/06/10)
A palladium-catalyzed multicomponent reaction of propargylic amines, alkynyl bromides and cesium hydrogen carbonate to access oxazolidinones is reported. In contrast to previous reports, only a slight excess of cesium hydrogen carbonate is used as a surrogate of carbon dioxide. The reaction gives access to oxazolidinones bearing alkyl- and aryl polysubstituted enynes in good yield and very high E stereoselectivity.
Efficient and Recyclable Cobalt(II)/Ionic Liquid Catalytic System for CO2 Conversion to Prepare 2-Oxazolinones at Atmospheric Pressure
Zhou, Zhi-Hua,Chen, Kai-Hong,He, Liang-Nian
supporting information, p. 1223 - 1228 (2019/11/21)
Converting CO2 into value-added chemicals represents a promising way to alleviate the CO2 derived environmental issues, for which the development of catalysts with high efficiency and recyclability is very desirable. Herein, the catalytic system by combining cobalt source and ionic liquid (IL) has been developed as the efficacious and recyclable catalyst for the carboxylative cyclization of propargylic amine and CO2 to prepare 2-oxazolinones. In this protocol, various propargylic amines were successfully transformed into the corresponding 2-oxazolinones with CoBr2 and diethylimidazolium acetate ([EEIM][OAc]) as the catalyst under atmospheric CO2 pressure. It is worth noting that the turnover number (TON) of this transformation can be up to 1740, presumably being attributed to the cooperative effect of the cobalt and IL. Furthermore, the existence of IL enables the catalytic system to be easily recycled to 10 times without losing its activity.
Palladium-Catalyzed Carbo-Oxygenation of Propargylic Amines using in Situ Tether Formation
Greenwood, Phillip D. G.,Grenet, Erwann,Waser, Jerome
supporting information, p. 3010 - 3013 (2019/02/07)
1,2-Amino alcohols and α-aminocarbonyls are frequently found in natural products, drugs, chiral auxiliaries, and catalysts. This work reports a new method for the palladium-catalyzed oxyalkynylation and oxyarylation of propargylic amines. The reaction is perfectly regioselective based on the in situ introduction of a hemiacetal tether derived from trifluoroacetaldehyde. cis-Selective carbo-oxygenation was achieved for terminal alkynes, whereas internal alkynes gave trans-carbo-oxygenation products. The obtained enol ethers could be easily transformed into 1,2-amino alcohols or α-amino ketones using hydrogenation or hydrolysis, respectively.
Construction of the Oxazolidinone Framework from Propargylamine and CO2 in Air at Ambient Temperature: Catalytic Effect of a Gold Complex Featuring an L2/Z-Type Ligand
Inagaki, Fuyuhiko,Maeda, Kakeru,Nakazawa, Kenta,Mukai, Chisato
, p. 2972 - 2976 (2018/06/27)
The metal-catalyzed carboxylation of propargylamines with aerial CO2 at room temperature to form 5-methyleneoxazolidin-2-one derivatives has been developed. In this reaction, the catalyst [Au(dpbF)]X featuring a Z-type ligand gave the best results, presumably due to the σ-acceptance of the borane atom.
Post-synthetically modified MOF for the A3-coupling reaction of aldehyde, amine, and alkyne
Kassymova, Meruyert,De Mahieu, Alaric,Chaemchuen, Somboon,Demeyere, Patrick,Mousavi, Bibimaryam,Zhuiykov, Serge,Yusubov, Mekhman S.,Verpoort, Francis
, p. 4129 - 4140 (2018/08/24)
A new heterogeneous NHC catalyst (Ag-NHC-MOF) was synthesized by the post-synthetic modification of an azolium-containing metal-organic framework. The structure of the catalyst was well defined and fully characterized using various techniques such as PXRD, FE-SEM, HR-TEM, XPS, FT-IR, TGA, BET, 1H-NMR, 13C-NMR, EDS, and ICP. The catalyst showed an excellent activity towards the A3-coupling reaction with a broad substrate scope. The A3-coupling reaction was performed under ambient conditions and full conversion was reached within just 1 hour for the model reaction. The heterogeneous silver NHC MOF (Ag-NHC-MOF) catalyst can be recycled and reused at least four times without a significant loss of activity. In comparison with previously reported heterogeneous catalysts applied for the A3-coupling reaction, the Ag-NHC-MOF demonstrates a superior performance for the A3-coupling reaction.
Site-Selective Labeling of Native Proteins by a Multicomponent Approach
Chilamari, Maheshwerreddy,Purushottam, Landa,Rai, Vishal
supporting information, p. 3819 - 3823 (2017/03/27)
Chemical functionalization of proteins is an indispensable tool. Yet, selective labeling of native proteins has been an arduous task. The limited success of chemical methods allows N-terminus protein labeling, but the examples with side-chain residues are rare. Herein, we surpass this challenge through a multicomponent transformation that operates under physiological conditions in the presence of a protein, aldehyde, acetylene, and Cu-ligand complex. The methodology results in the labeling of a single lysine residue in nine distinct proteins.
