29218-27-7Relevant academic research and scientific papers
Corrigendum to: Substrate-Controlled Product Divergence: Conversion of CO2into Heterocyclic Products (Angew. Chem. Int. Ed., (2016), 55, (3972–3976) 10.1002/anie.201511521)
Rintjema, Jeroen,Epping, Roel,Fiorani, Giulia,Martín, Eddy,Escudero-Adán, Eduardo C.,Kleij, Arjan W.
, p. 12136 - 12136 (2016)
Figure 2 of this Communication needs to be revised as shown below. Specifically, compounds 18 and 19 were erroneously exchanged from their position. The authors wish to apologize for this error. (Figure presented.).
Room Temperature Cu-Catalyzed N-Arylation of Oxazolidinones and Amides with (Hetero)Aryl Iodides
Bhunia, Subhajit,De, Subhadip,Ma, Dawei
supporting information, (2022/02/09)
N,N′-Bis(pyridin-2-ylmethyl)oxalamide (BPMO) was found to be an apposite promoter for the Cu-catalyzed N-arylation of oxazolidinones and primary and secondary amides with (hetero)aryl iodides at room temperature. Excellent chemoselectivity reached between
Microwave-Assisted Electrostatically Enhanced Phenol-Catalyzed Synthesis of Oxazolidinones
Al-Harrasi, Ahmed,Ebrahimi, Amirhossein,Golmohammadi, Farhad,Rostami, Ali,Sakhaee, Nader
, (2021/10/20)
An electrostatically enhanced phenol is utilized as a straightforward, sustainable, and potent one-component organocatalyst for the atom-economic transformation of epoxides to oxazolidinones under microwave irradiation. Integrating a positively charged center into phenols over a modular one-step preparation gives rise to a bifunctional system with improved acidity and activity, competent in rapid assembly of epoxides and isocyanates under microwave irradiation in a short reaction time (20-60 min). A careful assessment of the efficacy of various positively charged phenols and anilines and the impact of several factors, such as catalyst loading, temperature, and the kind of nucleophile, on catalytic reactivity were examined. Under neat conditions, this one-component catalytic platform was exploited to prepare more than 40 examples of oxazolidinones from a variety of aryl- and alkyl-substituted epoxides and isocyanates within minutes, where up to 96% yield and high degree of selectivity were attained. DFT calculations to achieve reaction barriers for different catalytic routes were conducted to provide mechanistic understanding and corroborated the experimental findings in which concurrent epoxide ring-opening and isocyanate incorporation were proposed.
Squaramide–Quaternary Ammonium Salt as an Effective Binary Organocatalytic System for Oxazolidinone Synthesis from Isocyanates and Epoxides
Rostami, Ali,Ebrahimi, Amirhossein,Husband, John,Anwar, Muhammad Usman,Csuk, Rene,Al-Harrasi, Ahmed
, p. 1881 - 1895 (2020/03/13)
Squaramide–quaternary ammonium salt is illustrated as a simple, tunable, and competent metal-free binary catalytic platform for the atom-economic conversion of epoxides and isocyanates into oxazolidinones. Although, various metal catalysts have been employed for the title reaction, application of organocatalysis is scarce. At first, a rational survey of catalytic activity of several air-stable and architecturally distinct squaramides was undertaken. Thereafter, the impact on catalytic capability of different parameters, such as temperature, catalyst loading, and nature of nucleophiles, was examined. This binary organocatalytic system for the oxazolidinone synthesis, composed of a squaramide entity along with a suitable halide anion, was applied to the challenging conversion of a plethora of alkyl- and aryl-substituted epoxides– including disubstituted and enantioenriched ones– and isocyanates into the corresponding oxazolidinones in high-to-excellent yields. The time-dependent formation of oxazolidinone from epoxide and isocyanate was monitored by FTIR-ATR and 1H NMR spectroscopy and the scalability of this process was also described. In light of 1H NMR experiment, a hydrogen-bonding/anion-binding mechanism was proposed wherein the nucleophilic ring-opening operation, and oxo- and carbamate-anions stabilization occur cooperatively towards isocyanate fixation.
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.
Stereocontrolled, Divergent, Al(lll)-Catalyzed Coupling of Chiral N-Aryl Epoxy Amines and CO2
Lee, Yuseop,Choi, Jonghoon,Kim, Hyunwoo
, p. 5036 - 5039 (2018/08/24)
A divergent coupling reaction was achieved between N-aryl epoxy amines and CO2. By using two different cocatalysts, tetrabutylammonium iodide (TBAI) or 4-dimethylaminopyridine (DMAP) together with an Al(III) Lewis acid, cyclic carbonates or oxazolidinones were selectively produced through two distinct reaction pathways, respectively. The proposed reaction mechanism was supported by the stereochemical determination of the products. A gram-scale production of Linezolid was successfully achieved.
Metal-Free Synthesis of Oxazolidine-2,4-diones and 3,3-Disubstituted Oxindoles via ICl-Induced Cyclization
Yi, Wei,Fang, Xing-Xiao,Liu, Qing-Yun,Liu, Gong-Qing
, p. 6671 - 6681 (2019/01/04)
A metal-free method for the construction of oxazolidine-2,4-diones and oxindoles was discussed. Using iodine monochloride (ICl) as both the reaction promoter and iodide source, the iodolactonization of N-Boc acrylamides proceeded readily and provided the corresponding iodo oxazolidine-2,4-diones and oxazolidin-2-ones in good isolated yields. The obtained oxazolidine-2,4-diones can be used as key intermediates in the synthesis of toloxatone. When N-alkyl-N-arylacrylamide derivatives were subjected to the same reaction, iodocarbocyclization products 3,3-disubstituted oxindoles were obtained. The obtained oxindoles can be used as key intermediates in the synthesis of the alkaloids (±)-esermethole and (±)-physostigmine.
Tetraarylphosphonium Salt-Catalyzed Synthesis of Oxazolidinones from Isocyanates and Epoxides
Toda, Yasunori,Gomyou, Shuto,Tanaka, Shoya,Komiyama, Yutaka,Kikuchi, Ayaka,Suga, Hiroyuki
, p. 5786 - 5789 (2017/11/10)
Preparation of a range of oxazolidinones, including enantioenriched N-aryl-substituted oxazolidinones, in which tetraarylphosphonium salts (TAPS) catalyze the [3 + 2] coupling reaction of isocyanates and epoxides effectively, is described. The key finding is a Br?nsted acid/halide ion bifunctional catalyst that can accelerate epoxide ring opening with high regioselectivity. Mechanistic studies disclosed that the ylide generated from TAPS, along with the formation of halohydrins, plays a crucial role in the reaction with isocyanates.
Direct synthesis of oxazolidin-2-ones from tert-butyl allylcarbamate via halo-induced cyclisation
Paisuwan, Waroton,Chantra, Thanakrit,Rashatasakhon, Paitoon,Sukwattanasinitt, Mongkol,Ajavakom, Anawat
, p. 3363 - 3367 (2017/05/22)
A novel synthetic pathway towards the 2-oxazolidinone derivatives involving the halo-induced cyclisation of tert-butyl allyl(phenyl)carbamate was successfully developed. Various halogenating reagents were evaluated under different reaction conditions for the reaction optimisation. Interestingly, the synthetic route to 2-oxazolidinone derivatives containing one halogen atom in the aliphatic site or two halogen atoms including the extra halogen atom substituted in the aryl group at the para position, were thoroughly established for all chloro-, bromo- and iodo compounds. Either halo-unsubstituted-aryl oxazolidinone or p-halo-substituted-aryl oxazolidinone could be selectively produced by selecting the appropriate choices of halogenated reagents and reaction conditions e.g. reaction time and temperature. Toloxatone, a commercial antidepressant, was successfully synthesized by using this developed method.
Substrate-Controlled Product Divergence: Conversion of CO2 into Heterocyclic Products
Rintjema, Jeroen,Epping, Roel,Fiorani, Giulia,Martín, Eddy,Escudero-Adán, Eduardo C.,Kleij, Arjan W.
, p. 3972 - 3976 (2016/03/19)
Substituted epoxy alcohols and amines allow substrate-controlled conversion of CO2 into a wide range of heterocyclic structures through different mechanistic manifolds. This new approach results in an unusual scope of CO2-derived products by initial activation of CO2 through either the amine or alcohol unit, thus providing nucleophiles for intramolecular epoxy ring opening under mild reaction conditions. Control experiments support the crucial role of the amine/alcohol fragment in this process with the nucleophile-assisted ring-opening step following an SNi pathway, and a 5-exo-tet cyclization, thus leading to heterocyclic scaffolds.
