- Synergetic activation of CO2by the DBU-organocatalyst and amine substrates towards stable carbamate salts for synthesis of oxazolidinones
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The development of an efficient methodology to transform CO2 into valuable chemicals has attracted increasing attention concerning the challenging issues of CO2-utilization. Herein, an efficient approach for the preparation of oxazolidinones from CO2, primary (aliphatic/aromatic) amines and 1,2-dichloroethane (or its derivatives) catalyzed by DBU organo-superbase was achieved with yields of 47-97% under mild conditions (80-100 °C, 12 h, 1.0 MPa CO2). Control experiments demonstrated that the formation of an ion-pair carbamate salt intermediate IS-B derived from the reaction of CO2, DBU (catalyst) and an amine (substrate) was the key step for this three-component reaction. The available DBU-amine-CO2 adduct intermediate (like IS-B-2) with fair stability will evolve into the thermodynamically stable product oxazolidinones upon attack of 1,2-dichloroethane (or its derivatives), along with the regeneration of the DBU catalyst. Alternatively, the decomposition of the DBU-aryl amine-CO2 adduct (like IS-B-1) with relatively poor stability also could result in the competitive substitution reaction of 1,2-dichloroethane (or its derivatives) with the aryl amine. This work provides insights into synergetic CO2-activation by the DBU-catalyst and a nucleophilic amine-substrate via the formation of robust carbamate salt intermediates responsible for the final production of oxazolidinones. This journal is
- Chen, Xiao-Chao,Liu, Ye,Lu, Yong,Yao, Yin-Qing,Zhao, Kai-Chun
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p. 7072 - 7082
(2021/11/17)
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- The catalytic system ‘Rhodamine B/additive’ for the chemical fixation of CO2
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The catalytic system ‘Rhodamine B/additive’ was introduced to promote the CO2 reactions. We synthesized various cyclic carbonates in good to excellent yields under the catalysis of rhodamine B and TBAB. A variety of 2-oxazolidinone derivatives were obtained in the presence of rhodamine B and DBU.
- Wu, Feng-tian,Wu, Ling,Cui, Chun-na
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- Catalytic Dealkylative Synthesis of Cyclic Carbamates and Ureas via Hydrogen Atom Transfer and Radical-Polar Crossover
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Guided by the transition-metal hydrogen atom transfer and radical-polar crossover concepts, we developed a functional-group-tolerant and scalable method for the synthesis of cyclic carbamates and ureas, which are found in the structures of bioactive compo
- Nagai, Takuya,Mimata, Nao,Terada, Yoshihiro,Sebe, Chikayoshi,Shigehisa, Hiroki
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supporting information
p. 5522 - 5527
(2020/07/24)
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- Bifunctional organocatalysts for the conversion of CO2, epoxides and aryl amines to 3-aryl-2-oxazolidinones
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A route to synthesize 3-aryl-2-oxazolidinones is developed, which is achieved through a three component reaction between CO2, aryl amines, and epoxides with a binary organocatalytic system composed of organocatalysts and DBU (1,8-diazabicyclo[5.4.0]undec-7-ene). The method allows wide scopes of epoxide and aryl amine substrates with various functional groups under mild reaction conditions. The control experiments indicate that a cyclic carbonate is formed via cycloaddition of epoxides with CO2, which further reacts with the β-amino alcohol originating from epoxides and aryl amines, resulting in the formation of 3-aryl-2-oxazolidinones finally.
- Xie, Ya-Fei,Guo, Cheng,Shi, Lei,Peng, Bang-Hua,Liu, Ning
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p. 3497 - 3506
(2019/04/14)
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- A Multicomponent Approach to Oxazolidinone Synthesis Catalyzed by Rare-Earth Metal Amides
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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.
- Zhou, Meixia,Zheng, Xizhou,Wang, Yaorong,Yuan, Dan,Yao, Yingming
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p. 5783 - 5787
(2019/04/14)
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- Enzyme- and ruthenium-catalyzed dynamic kinetic resolution involving cascade alkoxycarbonylations for asymmetric synthesis of 5-Substituted N-Aryloxazolidinones
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Asymmetric synthesis of N-aryloxazolidinones via dynamic kinetic resolution was developed. A ruthenium-based catalyst was used in the racemization of β-anilino alcohols, while Candida antarctica lipase B (CAL-B) was applied for two selective alkoxycarbony
- Zhang, Yang,Xie, Sheng,Yan, Mingdi,Ramstr?m, Olof
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p. 138 - 144
(2019/04/10)
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- Method for synthesizing N - aryl oxazolidine -2 - ketone compound by ionic liquid catalysis
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The invention discloses a method for catalytic synthesis of a N-aryloxazolane-2-one compound or a chiral N-aryloxazolane-2-one compound from an ionic liquid. The process of the preparation method is as follows: a catalytic amount of ionic liquid is added
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Paragraph 0031-0060
(2019/10/01)
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- Metal-Organic Framework MIL-101-NH2-Supported Acetate-Based Butylimidazolium Ionic Liquid as a Highly Efficient Heterogeneous Catalyst for the Synthesis of 3-Aryl-2-oxazolidinones
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A novel heterogeneous catalyst, the ionic liquid (IL) of 1-butyl-3-methylimidazolium acetate (BmimOAc) immobilized on MIL-101-NH2, denoted as IL(OAc-)-MIL-101-NH2, was prepared by the "ship-in-a-bottle" strategy. The IL of
- Chong,Wang,Cheng,Lv,Ji
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p. 495 - 503
(2019/01/14)
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- Synthesis of Oxazolidinones and Derivatives through Three-Component Fixation of Carbon Dioxide
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An effective three-component fixation of atmospheric CO2 with readily available 1,2-dichloroethane and aromatic amine toward oxazolidinones catalyzed by in situ NHC was developed. The reaction occurred in good to excellent yields with good gene
- Mei, Congmin,Zhao, Yibo,Chen, Qianwei,Cao, Changsheng,Pang, Guangsheng,Shi, Yanhui
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p. 3057 - 3068
(2018/06/04)
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- Carbon dioxide-based facile synthesis of cyclic carbamates from amino alcohols
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We report herein a straightforward general method for the synthesis of cyclic carbamates from amino alcohols and carbon dioxide in the presence of an external base and a hydroxyl group activating reagent. Utilizing p-toluenesulfonyl chloride (TsCl), the reaction proceeds under mild conditions, and the approach is fully applicable to the preparation of various high value-added 5- and 6-membered rings as well as bicyclic fused ring carbamates. DFT calculations and experimental results indicate a SN2-type reaction mechanism with high regio-, chemo-, and stereoselectivity.
- Niemi, Teemu,Fernández, Israel,Steadman, Bethany,Mannisto, Jere K.,Repo, Timo
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supporting information
p. 3166 - 3169
(2018/03/28)
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- Influence of the catalyst structure in the cycloaddition of isocyanates to oxiranes promoted by tetraarylstibonium cations
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In the context of our work on electron deficient group 15 cations as Lewis acid catalysts, we have synthesized the triflate salts of a series of tetraarylstibonium cations of general formula [ArSbPh3]+ with Ar = Mes (4+), o-(dimethylamino)phenyl (5+), and o-((dimethylamino)methyl)phenyl (6+). These new cationic antimony derivatives, along with the known [Ph4Sb]+ (1+), 1-naphthyltriphenylstibonium (2+), and [(Ant)SbPh3]+ (3+), have been evaluated as catalysts for the cycloaddition of oxiranes and isocyanates under mild conditions. While all stibonium cations favor the 3,4-oxazolidinone products, the reactivities of 5+ and 6+ are hindered by the ancillary amino donor which quenches the Lewis acidity of the antimony center. A comparison of the other stibonium cations shows that 4+ is the most selective catalyst.
- Yang, Mengxi,Pati, Nilanjana,Bélanger-Chabot, Guillaume,Hirai, Masato,Gabba?, Fran?ois P.
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supporting information
p. 11843 - 11850
(2018/09/10)
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- Synthesis of N-aryl-2-oxazolidinones from cyclic carbonates and aromatic amines catalyzed by bio-catalyst
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A convenient and effective method of synthesizing 3-aryl-2-oxazolidinones from cyclic carbonates and aryl amines catalyzed by bio-catalyst adenine in the presence of Et3N under solvent-free conditions is described. The protocol is suitable for the wide scope of substrates, e.g. cyclic carbonates with or without substitutes, and aryl amines with either electron-withdrawing or electron-donating group. The products were obtained in good to excellent yields under the optimal conditions, even in steric hindered cases. The effect of reaction time, temperature, loading of catalyst, and amount of starting materials in the reaction were investigated, and the reaction mechanism is discussed.
- Mei, Congmin,Zhao, Yibo,Zou, Ke,Cao, Changsheng,Pang, Guangsheng,Shi, Yanhui
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p. 2179 - 2194
(2017/12/28)
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- Conversion of Carbon Dioxide into Oxazolidinones Mediated by Quaternary Ammonium Salts and DBU
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A straightforward method to construct oxazolidinones through a three-component reaction involving CO2, epoxides, and amines promoted by a combination of Bu4NI and 1,8-diazabicyclo[5.4.0]undec-7-ene was developed. A wide range of aromatic and aliphatic amines and monosubstituted epoxides were converted into 3,5-disubstituted-2-oxazolidines in up to 95 % yield. This metal-free and easily available catalytic system was applicable to a broad range of substrates, including conventionally challenging ones such as aliphatic epoxides, at atmospheric pressure. Preliminary mechanistic studies suggested a reaction pathway involving β-amino alcohols.
- Lv, Min,Wang, Peng,Yuan, Dan,Yao, Yingming
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p. 4451 - 4455
(2017/12/26)
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- Selective Synthesis of 5-Substituted N-Aryloxazolidinones by Cycloaddition Reaction of Epoxides with Arylcarbamates Catalyzed by the Ionic Liquid BmimOAc
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A selective procedure for the synthesis of 5-substituted N-aryloxazolidinones by the coupling of epoxides with arylcarbamates catalyzed by ionic liquids has been developed. The effects of reaction time, reactant molar ratio, amount of catalyst, and temper
- Elageed, Elnazeer H. M.,Chen, Bihua,Wang, Binshen,Zhang, Yongya,Wu, Shi,Liu, Xiuli,Gao, Guohua
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supporting information
p. 3650 - 3656
(2016/07/28)
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- Lipase-catalyzed kinetic resolution of 3-phenyloxazolidin-2-one derivatives: Cascade O- and N-alkoxycarbonylations
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A lipase-catalyzed, cascade kinetic resolution protocol has been established for the synthesis of 3-phenyloxazolidin-2-one derivatives with up to excellent enantioselectivities (95% ee). Candida antarctica lipase B showed high catalytic activity and stere
- Zhang, Yang,Zhang, Yan,Xie, Sheng,Yan, Mingdi,Ramstr?m, Olof
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- DBU and DBU-Derived Ionic Liquid Synergistic Catalysts for the Conversion of Carbon Dioxide/Carbon Disulfide to 3-Aryl-2-oxazolidinones/[1,3]Dithiolan-2-ylidenephenyl- Amine
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An intermolecular synergistic catalytic combination of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and a DBU-derived bromide ionic liquid has been developed for the conversion of CO2, epoxides, and amines under metal- And solvent-free conditions. Various 3-aryl-2-oxazolidinones are produced in moderate to excellent yields within a short reaction time. NMR spectroscopy and DFT calculations demonstrate that DBU as a hydrogen bond acceptor and the ionic liquid as a hydrogen bond donor activate the substrates cooperatively by inducing hydrogen bonds to promote the reaction effectively. Based on these results, a possible reaction mechanism on the synergistic catalysis of DBU and the ionic liquid is proposed. In addition, the reaction of CS2, ethylene oxide, and aniline catalyzed by the combination of DBU and the DBU-derived ionic liquid also proceeds smoothly, which opens a hitherto unreported route to [1,3]dithiolan-2-ylidenephenylamine in a straightforward way.
- Wang, Binshen,Luo, Zhoujie,Elageed, Elnazeer H. M.,Wu, Shi,Zhang, Yongya,Wu, Xiaopei,Xia, Fei,Zhang, Guirong,Gao, Guohua
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p. 830 - 838
(2016/03/05)
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- Transformation of Carbon Dioxide into Oxazolidinones and Cyclic Carbonates Catalyzed by Rare-Earth-Metal Phenolates
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Rare-earth-metal complexes stabilized by amine-bridged tri(phenolato) ligands were developed, and their activities in catalyzing transformations of CO2 were studied. A series of terminal epoxides and challenging disubstituted epoxides were converted into the respective cyclic carbonates in the presence of CO2 in yields of 58 to 96 %. In addition, these rare-earth-metal complexes also showed good activities in catalyzing three-component reactions of anilines, epoxides, and CO2, which generated 5-substituted-3-aryl-2-oxazolidines in yields of 48 to 96 %, as a useful strategy to construct oxazolidinones.
- Xu, Bin,Wang, Peng,Lv, Min,Yuan, Dan,Yao, Yingming
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p. 2466 - 2471
(2016/08/24)
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- A nitrogen bridged three aryloxyacetic-based rare-earth metal compound and its preparation method and application
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The invention discloses a nitrogen bridged triaryloxy rare-earth compound, and a preparation method and catalytic application thereof. The general formula of the rare-earth compound is LLn(THF)3, and the chemical structural formula is disclosed in the spe
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Paragraph 0096; 0097; 0099
(2017/03/08)
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- Efficient synthesis of 2-oxazolidinones from epoxides and carbamates catalyzed by amine-functionalized ionic liquids
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A series of amine-functionalized ionic liquids were prepared and their catalytic performance was tested in the synthesis of 2-oxazolidinones from epoxides and carbamates. Under optimized reaction conditions, good to excellent yields of various 2-oxazolidinones were achieved with different epoxides and carbamates. Moreover, the amine-functionalized ionic liquid catalyst could be easily recovered and reused without significant loss in activity.
- Shang, Jianpeng,Li, Zuopeng,Su, Caina,Guo, Yong,Deng, Youquan
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p. 71765 - 71769
(2015/09/08)
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- Synthesis of Oxazolidinones from Epoxides and Isocyanates Catalyzed by Rare-Earth-Metal Complexes
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Rare-earth-metal complexes stabilized by an amino-bridged triphenolate ligand showed high efficiency in catalyzing the cycloaddition of isocyanates and epoxides in the presence of NBu4I under mild conditions. This strategy is applicable to both
- Wang, Peng,Qin, Jie,Yuan, Dan,Wang, Yaorong,Yao, Yingming
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p. 1145 - 1151
(2015/04/14)
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- One-pot conversion of carbon dioxide, ethylene oxide, and amines to 3-aryl-2-oxazolidinones catalyzed with binary ionic liquids
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An effective one-pot method for the conversion of carbon dioxide, ethylene oxide, and amines to 3-aryl-2-oxazolidinones has been developed. This one-pot method consists of two parallel reactions and a subsequent cascade reaction between the two products of the corresponding parallel reactions. Notably, the binary ionic liquids of 1-butyl-3-methyl-imidazolium bromide and 1-butyl-3-methyl-imidazolium acetate demonstrate a synergistic catalytic effect on this new strategy. 1-Butyl-3-methyl-imidazolium bromide is essential in two parallel reactions owing to the good nucleophilicity and leaving ability of bromide, and 1-butyl-3-methyl-imidazolium acetate plays a dominant role in the subsequent cascade reaction owing to the strong basicity of acetate. In addition, the binary ionic liquids can be used thrice without significant loss of catalytic activity. Copyright
- Wang, Binshen,Elageed, Elnazeer H.M.,Zhang, Dawei,Yang, Sijuan,Wu, Shi,Zhang, Guirong,Gao, Guohua
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p. 278 - 283
(2014/01/23)
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- VanadiumV(salen) catalysed synthesis of oxazolidinones from epoxides and isocyanates
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The combination of a vanadiumV(salen) complex V +O(salen) EtOSO3- and tetrabutylammonium bromide forms a highly active catalyst system for the reaction between epoxides and isocyanates leading to oxazolidinones.
- Beattie, Christopher,North, Michael
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p. 31345 - 31352
(2014/08/05)
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- Aza-crown ether complex cation ionic liquids: Preparation and applications in organic reactions
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Aza-crown ether complex cation ionic liquids (aCECILs) were devised, fabricated, and characterized by using NMR spectroscopy, MS, thermogravimetric differential thermal analysis (TG-DTA), elemental analysis and physical properties. These new and room-temperature ILs were utilized as catalysts in various organic reactions, such as the cycloaddition reaction of CO2 to epoxides, esterification of acetic acid and alcohols, the condensation reaction of aniline and propylene carbonate, and Friedel-Crafts alkylation of indole with aldehydes were investigated carefully. In these reactions, the ionic liquid exhibited cooperative catalytic activity between the anion and cation. In addition, the aza-[18-C-6HK][HSO4]2 was the best acidic catalyst in the reactions of esterification and Friedel-Crafts alkylation under mild reaction conditions. Jewel in the crown: Nine new and room-temperature aza-crown ether complex ionic liquids (aCECILs) composed of multiple cations and anions were fabricated through a convenient procedure (see scheme). Some of them were used as catalysts in various organic reactions, such as the cycloaddition reaction of CO2 to propylene oxide, esterification of acetic acid and alcohols, the condensation of aniline and propylene carbonate, and Friedel-Crafts alkylation of indole with aldehydes.
- Song, Yingying,Cheng, Chen,Jing, Huanwang
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p. 12894 - 12900
(2015/03/30)
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- [(Salcen)CrIII + Lewis base]-catalyzed synthesis of N-aryl-substituted oxazolidinones from epoxides and aryl isocyanates
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[(Salcen)CrIII + Lewis base] was found to be a highly active and selective catalyst system in the [2+3] cycloaddition between epoxides and isocyanates to form 5-oxazolidinones. The reaction proceeds to high yield under mild reaction conditions
- Paddock, Robert L.,Adhikari, Debashis,Lord, Richard L.,Baik, Mu-Hyun,Nguyen, Sonbinh T.
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supporting information
p. 15187 - 15190
(2014/12/11)
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- Bimetallic aluminum(salen) catalyzed synthesis of oxazolidinones from epoxides and isocyanates
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The bimetallic aluminum(salen) complex [Al(salen)]2O is shown to catalyze the synthesis of oxazolidinones from epoxides and isocyanates. The reaction is demonstrated to proceed with overall retention of epoxide stereochemistry, and both aromati
- Baronsky, Thilo,Beattie, Christopher,Harrington, Ross W.,Irfan, Reyhan,North, Michael,Osende, Javier G.,Young, Carl
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p. 790 - 797
(2013/06/27)
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- Samarium triiodide catalyzed cycloaddition of epoxides with isocyanates: A facile synthesis of oxazolidinones
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Oxazolidinones were synthesized in high yields via cycloaddition of epoxides with isocyanates catalyzed by samarium triiodide.
- Wu, Hua-Yue,Ding, Jin-Chang,Liu, Yun-Kui
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- Process for producing oxazolidin-2-one derivative
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An industrial process for preparing an oxazolidin-2-one derivative represented by the following general formula (3) wherein R1, R2, R3and R4are hydrogen atom, straight, branched or cyclic alkyl group, straight or branched alkyl group substituted by alkoxy, substituted amino or alkylthio, substituted or unsubstituted aralkyl group, or substituted or unsubstituted aryl group, and R5is are hydrogen atom, straight, branched or cyclic alkyl group, substituted or unsubstituted aralkyl group, or substituted or unsubstituted aromatic ring, which is characterized in reacting a 1,3-dioxolan-2-one derivative and a carbamate derivative or an urea derivative in the presence of a fluoride salt.
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- Selective Formation of α-Cleavage Cycloadduct of Oxirane with Heterocumulene Promoted by High-Coordinated Trialkyltin Complexes
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In the reaction of monosubstituted oxiranes and heterocumulenes, trialkyltin iodides coordinated by phosphine oxides effectively catalyzed the formation of heterocyles via cleavage at the substituted site in the oxirane ring, while other types of organotin complexes or noncomplexed organotin iodides promoted selective cleavage at the opposite site.A mechanistic investigation demonstrated that the coordination of phophine oxide promotes the reverse reaction of the oxirane-ring cleavage leading to the predominant formation of α-cleavage cycloadducts.
- Yano, Katsunori,Amishiro, Nobuyoshi,Baba, Akio,Matsuda, Haruo
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p. 2661 - 2667
(2007/10/02)
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- Regioselective Cycloaddition of 1,2-Disubstituted Aziridines to Heterocumulenes Catalyzed by Organoantimony Halides
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In the presence of catalytic amounts of organoantimony(V) halides such as Ph4SbI, Ph4SbBr, Ph3SbBr2, and Ph3SbCl2, the cycloaddition of aziridines 1a-g with heterocumulenes (phenyl isothiocyanate, carbon disulfide, and carbon dioxide) selectively gave ring-expanded cycloadducts 3a-d, f, g and 6e by α-cleavage of the aziridine rings. - Key Words: Organoantimony halides / Aziridines, cycloaddition of, α-cleavage of / Heterocumulenes
- Nomura, Ryoki,Nakano, Takahiro,Nishio, Yoshitaka,Ogawa, Sachiko,Ninagawa, Akira,Matsuda, Haruo
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p. 2407 - 2410
(2007/10/02)
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- Selective α-Cleavage Cycloaddition of Oxiranes with Heterocumulenes Catalyzed by Tetraphenylstibonium Iodide
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A catalytic amount of tetraphenylstibonium iodide (1) promoted unusual cycloadditions of oxiranes with isocyanates or carbodiimides, forming 3,4-disubstituted oxazolidin-2-ones 2 and oxazolidin-2-imines 4 under very mild conditions, respectively.In partic
- Fujiwara, Masahiro,Baba, Akio,Matsuda, Haruo
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p. 1351 - 1357
(2007/10/02)
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- UNUSUAL CYCLOADDITION OF OXIRANES WITH ISOCYANATES CATALYZED BY TETRAPHENYLSTIBONIUM IODIDE; SELECTIVE FORMATION OF 3,4-DISUBSTITUTED OXAZOLIDINONES.
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Tetraphenylstibonium iodide is a general and versatile catalyst for the selective formation of unusual cycloadducts, 3,4-disubstituted oxazolidinones, in the reaction of oxiranes with isocyanates.
- Baba, Akio,Fujiwara, Masahiro,Matsuda, Haruo
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- Cycloaddition Reaction of Heterocumulenes with Oxiranes Catalyzed by an Organotin Iodide-Lewis Base Complex
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Organotin halide-Lewis base complexes are versatile catalysts for the cycloaddition of heterocumulenes with oxiranes and afford good yields of five-membered heterocyclic compounds under mild and neutral conditions.The catalysts are sufficiently active tha
- Shibata, Ikuya,Baba, Akio,Iwasaki, Hiroyuki,Matsuda, Haruo
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p. 2177 - 2184
(2007/10/02)
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- The Cycloaddition of Isocyanates and Carbodiimides to Oxiranes Catalyzed by Organotin Iodide-Lewis Base Complexes
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Various types of five-membered heterocyclic compounds such as 2-iminodioxolanes, 2-oxazolidinones, and 2-iminooxazolidines, can be obtained from the cycloaddition of oxiranes with isocyanates or carbodiimides catalyzed by organotin iodide-Lewis base compl
- Baba, Akio,Shibata, Ikuya,Masuda, Kazuhiro,Matsuda, Haruo
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p. 1144 - 1146
(2007/10/02)
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