- Microwave-Assisted Electrostatically Enhanced Phenol-Catalyzed Synthesis of Oxazolidinones
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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.
- Rostami, Ali,Ebrahimi, Amirhossein,Sakhaee, Nader,Golmohammadi, Farhad,Al-Harrasi, Ahmed
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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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- Reaction Mechanism of CO2and Styrene Oxide Catalyzed by Ionic Liquids: A Combined DFT Calculation and Experimental Study
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Bioactive compound 3-aryl-2-oxazolidinone could be synthesized by a green method mixing carbon dioxide, aniline, and ethylene oxide. Our group previously proposed a parallel mechanism for this conversion catalyzed by ionic liquids. Recently, a new study o
- Chen, Jian,Ding, Tong,Gao, Guohua,Wang, Rong,Xia, Fei,Zha, Jinyin
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p. 7991 - 7998
(2020/11/27)
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- Triethylamine Hydroiodide as a Bifunctional Catalyst for the Solvent-Free Synthesis of 2-Oxazolidinones
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Among the wide variety of heterocycles, 2-oxazolidinones are recognized as some of the most important heterocyclic compounds in medicinal chemistry. Therefore, the development of a practical method for their synthesis would be an important development. He
- Nishiyori, Ryuichi,Okuno, Ken,Shirakawa, Seiji
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p. 4937 - 4941
(2020/07/30)
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- Squaramide–Quaternary Ammonium Salt as an Effective Binary Organocatalytic System for Oxazolidinone Synthesis from Isocyanates and Epoxides
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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.
- Rostami, Ali,Ebrahimi, Amirhossein,Husband, John,Anwar, Muhammad Usman,Csuk, Rene,Al-Harrasi, Ahmed
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p. 1881 - 1895
(2020/03/13)
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- Green synthesis of Dy2Ce2O7 Nanoparticles Immobilized on Fibrous Nano-silica for Synthesis of 3-Aryl-2-oxazolidinones from Alkenes, Amines, and Carbon Dioxide
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Abstract: In the present research, a new dendritic fibrous nanosilica (DFNS) based nanocatalyst (DFNS/Dy2Ce2O7) that has high surface zone as well as easy availability of active zones has been properly expanded using an easy approach. DFNS that possess high surface zone is functionalized by amino groups working as the anchors such that the nanoparticles of Dy2Ce2O7 are fine-dispersed onto the DFNS microspheres fibres, without any aggregation. The nanoparticles of Dy2Ce2O7 are produced by a green approach in the attendance of gum of ferula assa-foetida of Dy(NO3)3 and (NH4)2Ce(NO3)6 as ceric and dysprosium sources. The structural evaluation of the samples proved the synthesis of Dy2Ce2O7 NPs. Moreover, a straight way for the production of 3-aryl-2-oxazolidinones by carbon dioxide, olefins, and anilines was obtained utilizing nano catalyst of DFNS/Dy2Ce2O7 in the lack of solvent. The reaction works properly at moderate states. This method that is cheap and simple may be used to different olefins that has proper to excellent 3-aryl-2-oxazolidinones productions. The catalyst may be simply recycled for ten times without considerable losing the activity of its catalytic. Graphic Abstract: [Figure not available: see fulltext.]
- Feng, Li,Li, Xuhao,Xu, Chuang,Sadeghzadeh, Seyed Mohsen
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p. 1729 - 1740
(2020/01/03)
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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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supporting information
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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- 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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- Potassium phosphate-catalyzed one-pot synthesis of 3-aryl-2-oxazolidinones from epoxides, amines, and atmospheric carbon dioxide
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Potassium phosphate was found to be a highly active catalyst in the three-component cycloaddition of amines, epoxides, and carbon dioxide in DMF at ambient temperature to form 3-aryl-2-oxazolidinones. Atmospheric CO2 and a broad range of amines were employed in this transformation. Aryl isocyanate and 1,2-aminoalcohol were generated in situ as key intermediates. This one-pot reaction is applicable to a variety of terminal epoxides and amines. The key advantages are high yields, simple work-up, inexpensive catalysts, and a practical ten gram-scale synthesis.
- Seo, Ue Ryung,Chung, Young Keun
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p. 803 - 808
(2017/08/15)
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- Isocyanurate Formation During Oxazolidinone Synthesis from Epoxides and Isocyanates Catalysed by a Chromium(Salphen) Complex
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Chromium(salphen) complex 10 is found to be a catalyst for the preparation of oxazolidinones from epoxides and isocyanates. Using the optimal reaction conditions (1.5 mol % of chromium(salphen) complex 10 at 80 °C in toluene for 4 hours), six epoxides wer
- Wu, Xiao,Mason, Jess,North, Michael
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p. 12937 - 12943
(2017/09/25)
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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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- Tetraarylphosphonium Salt-Catalyzed Synthesis of Oxazolidinones from Isocyanates and Epoxides
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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.
- Toda, Yasunori,Gomyou, Shuto,Tanaka, Shoya,Komiyama, Yutaka,Kikuchi, Ayaka,Suga, Hiroyuki
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supporting information
p. 5786 - 5789
(2017/11/10)
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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 0124-0127
(2017/03/08)
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- Synthesis of Oxazolidinones from Epoxides and Isocyanates Catalysed by Aluminium Heteroscorpionate Complexes
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The combination of an aluminium(heteroscorpionate) complex and tetrabutylammonium bromide acts as a highly efficient catalyst system for the synthesis of oxazolidinones from epoxides and isocyanates. Twenty two complexes were tested derived from a range o
- Castro-Osma, José A.,Earlam, Amy,Lara-Sánchez, Agustín,Otero, Antonio,North, Michael
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p. 2100 - 2108
(2016/07/07)
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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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- 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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- 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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- 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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- Synthesis of chiral oxazolidinone derivatives through lipase-catalyzed kinetic resolution
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The synthesis of enantioenriched oxazolidinone derivatives through lipase-catalyzed kinetic resolution is described. The synthesis comprised a two-step, cascade acylation in one pot, resulting in a range of oxazolidinone derivatives in good yields and exc
- Zhang, Yan,Zhang, Yang,Ren, Yansong,Ramstr?m, Olof
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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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- Mechanistic investigation of the reaction of epoxides with heterocumulenes catalysed by a bimetallic aluminium salen complex
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The bimetallic aluminium(salen) complex [(Al(salen))2O] is known to catalyse the reaction between epoxides and heterocumulenes (carbon dioxide, carbon disulfide and isocyanates) leading to five-membered ring heterocycles. Despite their apparent
- Beattie, Christopher,North, Michael
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p. 8182 - 8188
(2014/07/07)
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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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- (Salen)chromium(III)/DMAP: An efficient catalyst system for the selective synthesis of 5-substituted oxazolidinones from carbon dioxide and aziridines
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(Equation Presented) (Salen)chromium(III)/DMAP was found to be an active catalyst system for the coupling of CO2 and aziridines. The oxazolidinone products were produced in high yield and selectivity from the opening of the aziridine at the most substituted N-C bond. This catalyst system worked well for a wide variety of monosubstituted N-aryl and N-alkyl aziridines as well as a 2,3-disubstituted N-alkyl aziridine.
- Miller, Aaron W.,Nguyen, SonBinh T.
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p. 2301 - 2304
(2007/10/03)
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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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- 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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