117416-53-2Relevant articles and documents
A metal-metalloporphyrin framework based on an octatopic porphyrin ligand for chemical fixation of CO2 with aziridines
Wang, Xun,Gao, Wen-Yang,Niu, Zheng,Wojtas, Lukasz,Perman, Jason A.,Chen, Yu-Sheng,Li, Zhong,Aguila, Briana,Ma, Shengqian
, p. 1170 - 1173 (2018)
A new porous metal-metalloporphyrin framework, MMPF-10, has been constructed from an octatopic porphyrin ligand, which links copper paddlewheel units to form a framework with fmj topology. In situ metallation of the porphyrin ligands provides MMPF-10 with two unique accessible Cu(ii) centers. This allows it to behave as an efficient Lewis acid catalyst in the first reported reaction of CO2 with aziridines to synthesize oxazolidinones catalyzed by an MMPF.
Activation of (salen)CoI complex by phosphorane for carbon dioxide transformation at ambient temperature and pressure
Zhou, Feng,Xie, Shi-Liang,Gao, Xiao-Tong,Zhang, Rong,Wang, Cui-Hong,Yin, Guang-Qiang,Zhou, Jian
, p. 3908 - 3915 (2017)
We report the activation of (salen)CoI complex 3g by a phosphorane to form a bifunctional catalyst for the reaction of carbon dioxide with terminal epoxides or aziridines at ambient temperature and 1 bar carbon dioxide pressure. Only 1.0 mol% of both (salen)CoI 3g and phosphorane 4d are required for cyclic carbonate synthesis, and the catalyst loading could even be lowered down to 0.1 mol%. Under these conditions, no polycarbonate formation is detected by NMR analysis. It is proposed that the high efficiency originates from the activation of (salen)CoI by a phosphorane to form a phosphorane-salen Co(iii) complex with enhanced Lewis acidity for the electrophilic activation while generating an iodide anion as a Lewis base co-catalyst to facilitate the ring-opening of epoxides. Further investigation revealed that the phosphorane-(salen)CoI complex could also successfully catalyze the coupling of CO2 with aziridines under ambient conditions at a catalyst loading of 2.5 mol%.
The solvent-free and catalyst-free conversion of an aziridine to an oxazolidinone using only carbon dioxide
Phung, Chau,Ulrich, Rani M.,Ibrahim, Mostafa,Tighe, Nathaniel T. G.,Lieberman, Deborah L.,Pinhas, Allan R.
, p. 3224 - 3229 (2011)
It has been found for the first time at room temperature that the reaction of an unactivated 2-alkyl or 2-aryl aziridine with carbon dioxide to generate the corresponding oxazolidinone does not need any form of catalysis or solvent to proceed in high yiel
Bifunctional aluminum catalyst for CO2 fixation: Regioselective ring opening of three-membered heterocyclic compounds
Ren, Wei-Min,Liu, Ye,Lu, Xiao-Bing
, p. 9771 - 9777 (2014)
Regioselective ring opening of three-membered heterocyclic compounds (epoxides or N-substituted aziridines) at various temperatures was observed in coupling reactions with CO2 by the use of an aluminum - salen catalyst in conjunction with intramolecular quaternary ammonium salts as cocatalysts, affording the corresponding five-membered cyclic products with complete configuration retention at the methine carbon. Notably, this bifunctional aluminum-based catalyst exhibited nearly 100% regioselectivity for the ring opening at the methylene C-O bond for various terminal epoxides. This was true for those bearing an electron-withdrawing group, such as styrene oxide or epichlorohydrin, thereby affording the synthesis of various enantiopure cyclic carbonates that have previously been obtained only rarely by other methods. An intramolecular cooperative catalysis is suggested to contribute to the high activity and excellent stereochemistry control observed. Surprisingly, the highly selective ring opening at the methine carbon of N-substituted aziridines was found in the coupling with CO2, predominantly giving 5-substituted oxazolininones with retention of configuration as a result of double inversion at the methine carbon. (Chemical Equation Presented).
The use of NMR chemical shifts to predict reaction pathways: Methanol formation from oxazolidinones
Froehlich, Joerg,Berger, Stefan
, p. 1632 - 1634 (2008)
The reduction of various N-substituted oxazolidin-2-ones with LiAlH 4 was investigated to open a pathway for methanol formation. By 15N and 13C NMR analysis and correlation with Hammett σp parameters appropriate substituents can be found which direct the reduction into the desired pathway. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
A Multicomponent Route to Functionalized Amides and Oxazolidinones
McPherson, Christopher G.,Cooper, Alasdair K.,Bubliauskas, Andrius,Mulrainey, Paul,Jamieson, Craig,Watson, Allan J. B.
, p. 6736 - 6739 (2017)
An organobase-mediated multicomponent reaction of unactivated esters, epoxides, and amines is reported, furnishing functionalized amide derivatives. A wide range of substrates are tolerated under the reaction conditions, including chiral epoxides, which react with no erosion of enantiopurity. Facile modification of the method through replacing the ester derivative with dimethyl carbonate enables access to the corresponding oxazolidinone derivatives.
Valorization of CO2 into N-alkyl Oxazolidin-2-ones Promoted by Metal-Free Porphyrin/TBACl System: Experimental and Computational Studies
Damiano, Caterina,Gallo, Emma,Manca, Gabriele,Sonzini, Paolo
, p. 2807 - 2814 (2021/06/25)
The cycloaddition of CO2 to N-alkyl aziridines was efficiently promoted by the convenient TPPH2/TBACl binary catalytic system. The metal-free procedure was effective for the synthesis of differently substituted N-alkyl oxazolidin-2-o
A Multicomponent Approach to Oxazolidinone Synthesis Catalyzed by Rare-Earth Metal Amides
Zhou, Meixia,Zheng, Xizhou,Wang, Yaorong,Yuan, Dan,Yao, Yingming
, p. 5783 - 5787 (2019/04/14)
Three-component reaction of epoxides, amines, and dimethyl carbonate catalyzed by rare-earth metal amides has been developed to synthesize oxazolidinones. 47 examples of 3,5-disubstituted oxazolidinones were prepared in 13–97 % yields. This is a simple and most practical method which employs easily available substrates and catalysts, and is applicable to a wide range of aromatic and aliphatic amines, as well as mono-substituted epoxides. Scope of disubstituted epoxides is rather limited, which requires further study. Preliminary mechanistic study reveals two possible reaction pathways through intermediates of β-amino alcohols or amides.
Synthesis of Oxazolidinones by using Carbon Dioxide as a C1 Building Block and an Aluminium-Based Catalyst
Sengoden, Mani,North, Michael,Whitwood, Adrian C.
, p. 3296 - 3303 (2019/07/05)
Oxazolidinone synthesis through the coupling of carbon dioxide and aziridines was catalysed by an aluminium(salphen) complex at 50–100 °C and 1–10 bar pressure under solvent-free conditions. The process was applicable to a variety of substituted aziridines, giving products with high regioselectivity. It involved the use of a sustainable and reusable aluminium-based catalyst, used carbon dioxide as a C1 source and provided access to pharmaceutically important oxazolidinones as illustrated by a total synthesis of toloxatone. This protocol was scalable, and the catalyst could be recovered and reused. A catalytic cycle was proposed based on stereochemical, kinetic and Hammett studies.
Ruthenium Porphyrin Catalyzed Synthesis of Oxazolidin-2-ones by Cycloaddition of CO2 to Aziridines
Carminati, Daniela,Gallo, Emma,Damiano, Caterina,Caselli, Alessandro,Intrieri, Daniela
, p. 5258 - 5262 (2019/01/04)
The reaction between N-substituted-2-arylaziridines and CO2 is efficiently promoted by ruthenium(VI) imidoporphyrin complexes and yields a mixture of 5-aryl (A) and 4-aryl (B) substituted oxazolidin-2-ones with a regioisomeric A/B ratio up to 9
