18292-76-7Relevant articles and documents
Synthesis of Ester- and Phosphonate-Functionalized AuI–Imidazolylidene Chlorides through the Isonitrile Route
Wurm, Thomas,Hornung, Julius,O'Neill, Matthew,Rudolph, Matthias,Rominger, Frank,Hashmi, A. Stephen K.
, p. 5143 - 5147 (2017)
Starting from DMSAuCl, isonitriles and functionalized propargylammonium salts in the presence of simple trimethylamine as auxiliary base, unsymmetrically substituted ester- and phosphonate-functionalized AuI–imidazolylidene complexes were synthesized in an easy-to-use modular one-pot template synthesis. In the course of the reaction, after the initial nucleophilic addition of the amine to the gold(I)-activated isonitrile, a Michael addition closes the N-heterocyclic carbene (NHC) ring. Then the remaining double bond migrates into the NHC ring, evidently a more stable position than the initial exocyclic double bond. These functional groups attached to the back bone of the NHC ligands represent ideal handles for a further modification of the system, for example an attachment to larger assemblies or heterogenization by an attachment to surfaces are conceivable.
One-step asymmetric synthesis of (R)- and (S)-rasagiline by reductive amination applying imine reductases
Matzel,Gand,H?hne
, p. 385 - 389 (2017)
Imine reductases (IREDs) show great potential as catalysts for reductive amination of ketones to produce chiral secondary amines. In this work, we explored this potential and synthesized the pharmaceutically relevant (R)-rasagiline in high yields (up to 81%) and good enantiomeric excess (up to 90% ee) from the ketone precursor. This one-step approach in aqueous medium represents the shortest synthesis route from achiral starting materials. Furthermore, we demonstrate for the first time that tertiary amines also can be accessed by this route, which provides new opportunities for eco-friendly enzymatic asymmetric syntheses of these important molecules.
Non-Noble-Metal Metal-Organic-Framework-Catalyzed Carboxylative Cyclization of Propargylic Amines with Atmospheric Carbon Dioxide under Ambient Conditions
Gu, Ai-Ling,Wang, Wan-Ting,Cheng, Xin-Yu,Hu, Tian-Ding,Wu, Zhi-Lei
supporting information, p. 13425 - 13433 (2021/08/30)
The coupling reaction of propargylic amines and carbon dioxide (CO2) to synthesize 2-oxazolidinones is an important reaction in industrial production, and yet harsh reaction conditions and noble-metal catalysts are often required to achieve high product yields. Herein, one novel noble-metal-free three-dimensional framework, [Mg3Cu2I2(IN)4(HCOO)2(DEF)4]n (1), assembled by magnesium and copper clusters was synthesized and applied to this reaction. Compound 1 displays excellent solvent stability. Importantly, 1, acting as heterogeneous catalyst, can highly catalyze the cyclization of propargylic amines with CO2 under atmospheric pressure at room temperature, which can be recycled at least five times without an obvious decrease of the catalytic activity. NMR spectroscopy, coupled with 13C-isotope- and deuterium-labeling experiments, clearly clarifies the mechanism of this catalytic system: CO2 was successfully captured and converted to the product of 2-oxazolidinones, the CC bond of propargylic amines can be effectively activated by 1, and proton transfer was involved in the reaction process. Density functional theory calculations are further conducted to uncover the reaction path and the crucial role of compound 1 during the reaction.
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.
