- Rational design 2-hydroxypropylphosphonium salts as cancer cell mitochondria-targeted vectors: Synthesis, structure, and biological properties
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It has been shown for a wide range of epoxy compounds that their interaction with triphenylphosphonium triflate occurs with a high chemoselectivity and leads to the formation of (2-hydroxypropyl)triphenylphosphonium triflates 3 substituted in the 3-position with an alkoxy, alkylcarboxyl group, or halogen, which were isolated in a high yield. Using the methodology for the disclosure of epichlorohydrin with alcohols in the presence of boron trifluoride ether-ate, followed by the substitution of iodine for chlorine and treatment with triphenylphosphine, 2-hydroxypropyltriphenylphosphonium iodides 4 were also obtained. The molecular and supramolec-ular structure of the obtained phosphonium salts was established, and their high antitumor activity was revealed in relation to duodenal adenocarcinoma. The formation of liposomal systems based on phosphonium salt 3 and L-α-phosphatidylcholine (PC) was employed for improving the bioavailabil-ity and reducing the toxicity. They were produced by the thin film rehydration method and exhibited cytotoxic properties. This rational design of phosphonium salts 3 and 4 has promising potential of new vectors for targeted delivery into mitochondria of tumor cells.
- Amerhanova, Syumbelya K.,Dimukhametov, Mudaris N.,Gubaidullin, Aidar T.,Islamov, Daut R.,Litvinov, Igor A.,Lyubina, Anna P.,Mironov, Vladimir F.,Nemtarev, Andrey V.,Pashirova, Tatiana N.,Titov, Eugenii A.,Tsepaeva, Olga V.,Voloshina, Alexandra D.
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- MBA-cross-linked poly(N-vinyl-2-pyrrolidone)/ferric chloride macromolecular coordination complex as a novel and recyclable Lewis acid catalyst: Synthesis, characterization, and performance toward for regioselective ring-opening alcoholysis of epoxides
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A novel macromolecular-metal coordination complex, MBA-cross-linked PNVP/FeCl3 material was fabricated by immobilization of water intolerant ferric chloride onto the porous cross-linked poly(N-vinyl-2-pyrrolidone) carrier beads as a macromolecular ligand or carrier which was prepared by suspension free-radical copolymerization of N-vinyl-2-pyrrolidone (NVP) and N,N′-methylene bis-acrylamide (MBA) as a crosslinking agent in water. The obtained PNVP/FeCl3 was characterized by UV/vis and FT-IR spectroscopies, TGA, FE-SEM, EDX, and ICP techniques. This heterogenized version of ferric chloride is a convenient and safe alternative to highly water intolerant ferric chloride. The catalytic performance of (PNVP/FeCl3) as an efficient and recyclable polymeric Lewis acid catalyst was appropriately probed in the regio-and stereoselective nucleophilic ring opening of various epoxides with various alcohols in excellent yields with TOF up to 182.48 h?1 without generating any waste. The activity data indicate that this heterogeneous catalyst is very active and could be easily recovered, and reused at least six times without appreciable loss of activity indicating its stability under experimental conditions.
- Rahmatpour, Ali,Zamani, Maryam
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- Readily Scalable Methodology for the Synthesis of Nonsymmetric Glyceryl Diethers by a Tandem Acid-/Base-Catalyzed Process
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A useful optimized synthetic methodology has been designed for the synthesis of nonsymmetric glyceryl diethers from epichlorohydrin. A tandem process combining a cheap, heterogeneous, and fully recoverable acid catalyst and alkaline hydroxide is used for the synthesis of a variety of glycerol-derived ethers bearing different alkyl substituents in 1 and 3 positions. Different heterogeneous acid catalysts have been tested for the reaction of epichlorohydrin with several alcohols, the best results being obtained with readily available recoverable and inexpensive montmorillonite-K10 and Nafion NR50. For the second reaction step, potassium hydroxide is used. In all the cases, good yields of the desired glyceryl diethers are obtained in smooth reaction conditions, always with total conversion of epichlorohydrin and without the need of intermediate purification. Scale-up of the tandem process has been carried out with good results.
- Leal-Duaso, Alejandro,Gracia-Barberán, Sara,Mayoral, José A.,Garciá, José I.,Pires, Elisabet
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p. 154 - 162
(2020/02/04)
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- Fiber-supported Fe(iii) complex catalyst in spinning basket reactor for cleaner ring-opening of epoxides with alcohols
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Herein, a newly designed fiber-supported iron catalyst was successfully synthesized by rooting diamine ligands into the surface layer of commercially available polyacrylonitrile fiber and then utilizing the diamine groups to immobilize Fe(iii) ions for heterogeneous catalytic ring-opening reactions. The resulting materials were characterized and observed in detail by elemental analysis, mechanical properties, FTIR spectroscopy and morphology during both the preparation and the utilization processes. Moreover, the fiber catalyst was used in the spinning basket reactor-mediated ring-opening of various epoxides by a series of alcohols under mild reaction conditions, giving good to quantitative yields of the corresponding β-alkoxy alcohols. In addition, the fiber catalyst in the impellers of the agitation system was shown to be reusable multiple times without leaching of the Fe(iii) ions, and when stored on the shelf remained equally active for at least three months. Furthermore, the catalytic system was convenient and effective for scaling-up experiments and thereby has prospects in industrial applications.
- Shi, Xian-Lei,Sun, Benyu,Hu, Qianqian,Chen, Yongju,Duan, Peigao
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p. 3573 - 3582
(2019/07/09)
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- An epoxide ring-opening reaction by using sol–gel-synthesized palladium supported on a strontium hydroxyl fluoride catalyst
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Palladium supported on a strontium hydroxyl fluoride catalyst was synthesized by a one-pot fluorolytic sol–gel method. The prepared catalyst was characterized by various physicochemical techniques. The sol–gel method has led to the formation of a high surface area (57?m2g?1), mesoporous (pore diameter?=?13.0?nm) catalyst with uniform dispersion of Pd nanoparticles of size ～7?nm on the surface of strontium hydroxyl fluoride. The catalyst was used for epoxide alcoholysis, and 100% conversion was obtained with 96% selectivity for β-alkoxy alcohols under mild conditions. The catalyst could be recycled for up to three catalytic cycles without any appreciable decrease in conversion and selectivity, indicating the stability of the catalyst under the reaction conditions. Further, the mechanism of alcoholysis was proposed on the basis of the physicochemical characteristics of the catalyst and on the basis of the products formed during the catalytic reaction.
- Acham, Vaibhav R.,Dongare, Mohan K.,Kemnitz, Erhard,Umbarkar, Shubhangi B.
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p. 1237 - 1246
(2016/10/13)
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- Enhanced metal loading in SBA-15-type catalysts facilitated by salt addition: Synthesis, characterization and catalytic epoxide alcoholysis activity of molybdenum incorporated porous silica
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We report a novel method to increase the metal loading in SBA-15 silica matrix via direct synthesis. It was demonstrated through the synthesis and characterization of a series of molybdenum containing SBA-15 mesoporous silica catalysts prepared with and without diammonium hydrogen phosphate (DHP) as an additive. Catalysts prepared with DHP show a 2-3 times increase in incorporation of molybdenum in the silica matrix and pore size enlargement. The synthesized catalysts were characterized using nitrogen sorption, X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma-optical emission spectroscopy (ICP-OES). The catalytic activity of catalysts prepared with DHP for alcoholysis of epoxides was superior than the catalyst prepared without DHP. Alcoholysis of epoxides was demonstrated for a range of alcohols and epoxides under ambient conditions in as little as 30 min with high selectivity.
- Budhi, Sridhar,Peeraphatdit, Chorthip,Pylypenko, Svitlana,Nguyen, Vy H.T.,Smith, Emily A.,Trewyn, Brian G.
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p. 469 - 476
(2014/03/21)
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- Nucleophilic reactivity of ethers against terminal epoxides in the presence of BF3: A mechanistic study
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In the presence of BF3, a series of symmetrical and unsymmetrical ethers reacted with epichlorohydrin and 2-[(benzyloxy)methyl] oxirane, two terminal epoxides, to afford 1-alkoxy-3-chloropropan-2-ol and 1-alkoxy-3-(benzyloxy)propan-2-ol. The cleavage of unsymmetrical ethers occurred via an SN2 or SN1 mechanism. Secondary epoxides did not give similar ring-opening products. Copyright
- Kose, Aytekin,Altundas, Ramazan,Secen, Hasan,Kara, Yunus
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p. 1325 - 1330
(2013/08/23)
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- Efficient and regioselective ring-opening of epoxides with alcohols and sodium azide by using catalytic amounts of gacl3/polyvinylpyrrolidone
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A new polymeric catalyst was prepared by supporting GaCl3 on cross-linked polyvinylpyrrolidone (GaCl3/ PVP). This catalyst was employed for efficient and regioselective ring-opening reaction of epoxides by various alcohols under solvent-free conditions at room temperature. In our procedure, this heterogeneous catalyst was used at neutral and mild reaction conditions to afford high yields of β-alkoxy alcohols. Also, regioselective conversion of epoxides to β-azidohydrines was accomplished by sodium azide in MeOH in the presence of GaCl3/PVP at room temperature. GaCl3/PVP is a non-hygroscopic and recoverable catalyst and is easily separated from reaction mixture by a simple filtration and re-used repeatedly. Also, this catalyst has good handling and can be stored for long time without any reducing of its reactivity.
- Pourali, Ali Reza,Ghayeni, Samaneh,Afghahi, Fatemeh
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p. 1741 - 1744
(2013/07/26)
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- Mild and efficient ring opening of epoxides catalyzed by potassium dodecatungstocobaltate(III)
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Efficient ring opening of epoxides under mild conditions is reported. Potassium dodecatungstocobaltate(III) trihydrate was used as an efficient catalyst for the alcoholysis and acetolysis of epoxides. Conversion of epoxides to thiiranes was also performed efficiently in the presence of this catalyst. Springer-Verlag 2005.
- Tangestaninejad, Shahram,Moghadam, Majid,Mirkhani, Valiollah,Yadollahi, Bahram,Mirmohammadi, S. Mohammad R.
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p. 235 - 242
(2007/10/03)
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- Synthesis of 1-alkoxy-3-N-succinimido-2-propanols
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Procedures for preparing 1-alkoxy-3-chloro-2-propanols, with their subsequent transformation to 1-alkoxy-N-succinimido-2-propanols, were developed.
- Gasanov,Allakhverdiev
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p. 2026 - 2028
(2007/10/03)
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- Difluorocarbene induced of facile synthesis of chlorohydrins from glycidyl ethers
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A novel and unusual approach based on a ClCF2COONa-DMF system has been developed for the synthesis of chlorohydrins via an unexpected mechanism. In a first ever report for the synthesis of chlorohydrins from glycidyl ethers, e.g., CH2=CH-CH2-O-Z, CH 3CH2-O-Z, C6H5-O-Z, C 6H4(o-CH3)-O-Z, CH2=C(CH 3)C(=O)-O-Z, etc., (where Z = glycidyl), difluorocarbene-induced facile regioselective ring opening of epoxides has generated the compound in high yield (70%-83%).
- Singh, Sapna,Bhadury, Pinaki S.,Sharma, Mamta,Palit, Meehir,Jaiswal, Devendra K.
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p. 1249 - 1253
(2007/10/03)
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- Rapid and efficient ring opening of epoxides catalyzed by a new electron deficient tin(IV) porphyrin
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The new electron deficient tin(IV) tetraphenylporphyrinato trifluoromethanesulfonate, [SnIV(tpp)(OTf)2], was used as an efficient catalyst for the alcoholysis, hydrolysis and acetolysis of epoxides. Conversion of epoxides to thiiranes and acetonides were also performed efficiently in the presence of this catalyst.
- Moghadam, Majid,Tangestaninejad, Shahram,Mirkhani, Valiollah,Shaibani, Reza
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p. 6105 - 6111
(2007/10/03)
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- Efficient regio- and stereoselective ring opening of epoxides with alcohols, acetic acid and water catalyzed by ammonium decatungstocerate(IV)
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Epoxides can be cleaved in a regio- and stereoselective manner under neutral conditions with alcohols and acetic acid in the presence of catalytic amounts of decatungstocerate(IV) ion, ([CeW10O36] 8-), affording the corresponding β-alkoxy and β-acetoxy alcohols in high yields. In water, ring opening of epoxides occurs with this catalyst to produce the corresponding diols in good yields.
- Mirkhani, Valiollah,Tangestaninejad, Shahram,Yadollahi, Bahram,Alipanah, Ladan
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p. 8213 - 8218
(2007/10/03)
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- Iron perchlorate on silica gel as multi-purpose reagent for catalysis of closure and rupture of carbon-oxygen bond in epoxides, alcohols, and esters
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Aliphatic alcohols and water in the presence of catalytic amounts of Fe3+ ion introduced as iron(III) perchlorate on silica gel carrier perform efficient regiospecific opening of an epoxy ring. Carbon acids esterification with various type alcohols was carried out using the system Fe(ClO4)3-silica gel in dichloromethane under conditions excluding solvolysis. Acetylation and formylation of alcohols was performed by efficient transesterification with ethyl acetate and ethyl formate.
- Salechi,Khodaei,Ghareghani,Motlagh
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p. 794 - 796
(2007/10/03)
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- Mechanism of preferential enrichment, an unusual enantiomeric resolution phenomenon caused by polymorphic transition during crystallization of mixed crystals composed of two enantiomers
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The mechanism of Preferential Enrichment, an unusual enantiomeric resolution phenomenon observed upon recrystallization of a series of racemic crystals which are classified as a racemic mixed crystal with fairly ordered arrangement of the two enantiomers, has been studied. On the basis of the existence of polymorphs and the occurrence of the resulting polymorphic transition during crystallization from solution, the mechanism has been accounted for in terms of (1) a preferential homochiral molecular association to form one-dimensional chain structures in the supersaturated solution of the racemate or nonracemic sample with a low ee value, (2) a kinetic formation of a metastable crystalline phase retaining the homochiral chain structures in a process of nucleation, (3) a polymorphic transition from the metastable phase to a stable one followed by enantioselective liberation of the excess R (or S) enantiomers from the transformed crystal into solution at the beginning of crystal growth to result in a slight enrichment (up to 10% ee) of the opposite S (or R) enantiomer in the deposited crystals, together with an enantiomeric enrichment of the R (or S) enantiomer in the mother liquor, and (4) a chiral discrimination by the once formed S (or R)-rich stable crystalline phase in a process of the subsequent crystal growth, leading to a considerable enantiomeric enrichment of the R (or S) enantiomer up to 100% ee in the mother liquor. The processes (3) and (4) are considered to be directly responsible for an enrichment of one enantiomer in the mother liquor. The association mode of the two enantiomers in solution has been investigated by means of (i) the solubility measurement and (ii) the number-averaged molecular weight measurement in solution by vapor pressure osmometry, together with (iii) the molecular dynamics simulation of oligomer models. The polymorphic transition during crystallization has been observed visually and by means of the in situ FTIR technique and DSC measurement. Both metastable and stable crystals have been obtained, and their crystal structures have been elucidated by X-ray crystallographic analysis of their single crystals.
- Tamura, Rui,Fujimoto, Daisuke,Lepp, Zsolt,Misaki, Kentaro,Miura, Hideyuki,Takahashi, Hiroki,Ushio, Takanori,Nakai, Tadashi,Hirotsu, Ken
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p. 13139 - 13153
(2007/10/03)
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- Bismuth(III) chloride (BiCl3); an efficient catalyst for mild, regio- and stereoselective cleavage of epoxides with alcohols, acetic acid and water
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Epoxides can be cleaved in a regio- and stereoselective manner with alcohols, acetic acid and water in the presence of catalytic amounts of bismuth(III) chloride, affording the corresponding β-alkoxy and β-acetoxy alcohols and diols in high yields.
- Mohammadpoor-Baltork,Tangestaninejad,Aliyan,Mirkhani
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p. 2365 - 2374
(2007/10/03)
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- Ferric perchlorate: An efficient reagent for regio- and stereoselective alcoholysis and hydrolysis of epoxides
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Regio- and stereoselective ring opening reaction of epoxides is achieved efficiently by aliphatic alcohols and water in the presence of catalytic amounts of ferric perchlorate.
- Salehi, Peyman,Seddighi, Behnam,Irandoost, Mohsen,Kargar Behbahani, Farahnaz
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p. 2967 - 2973
(2007/10/03)
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- Highly efficient, regio- and stereoselective ring opening of epoxides and thiiranes with Ce(OTf)4
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Ceric triflate, Ce(OTf)4 is used as an efficient catalyst for ring opening of epoxides in the presence of alcohols, water, and acetic acid. The reactions proceed with high regio and stereoselectivity and in excellent yields. The reaction of R(+) styrene oxide with methanol occurs with excellent optical purity. Ring opening of thiiranes in alcohols, water and acetic acid followed by dimerisation to the corresponding disulfides occur efficiently in the presence of this reagent. A mild method for the preparation of dithianes from thiiranes and Ce(OTf)4 is also described.
- Iranpoor,Shekarriz,Shiriny
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p. 347 - 366
(2007/10/03)
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- Highly efficient, regio- and stereoselective alcoholysis of epoxides catalyzed with iron(III) chloride
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An efficient, catalytic, simple and mild method for the conversion of epoxides into their corresponding β-alkoxy alcohols was performed in primary, secondary and tertiary alcohols and in the presence of catalytic amounts of ferric chloride. The β-alkoxy alcohols were obtained with high stereo- and regioselectivity and in good to excellent yields.
- Iranpoor,Salehi
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p. 1152 - 1154
(2007/10/02)
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- 2,3-Dichloro-5,6-dicyano-p-benzoquinone, an efficient, mild, neutral and highly regioselective catalyst for alcoholysis of epoxides
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Ring-opening reactions of epoxides with catalytic amounts of 2,3- Dichloro-5,6-Dicyano-p-Benzoquinone (DDQ) are performed with high regioselectivity under neutral conditions, in primary, secondary and tertiary alcohols as solvents and nucleophiles. The corresponding β- alkoxy alcohols were obtained in excellent yields.
- Iranpoor,Mohammadpour Baltork
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p. 735 - 738
(2007/10/02)
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- Mild, Efficient and Selective Opening of Epoxides with Alcohols Catalyzed by Ceric(IV) Ammonium Nitrate
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Commercially available Ceric(IV) Ammonium Nitrate (CAN) catalyzes nucleophilic ring opening of epoxides in primary, secondary and tertiary alcohols under mild conditions.The corresponding β-alkoxy-alcohols were obtained with high regio and stereoselectivity in high yields.
- Iranpoor, N.,Baltork, I. Mohammadpour
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p. 2789 - 2797
(2007/10/02)
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- ALCOOLYSE DE L'EPICHLORHYDRINE DU GLYCEROL SUR CATALYSEUR SOLIDE. SYNTHESE COMMODE D'ETHERS DU CHLORO-3 PROPANE DIOL-1,2.
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Monoethers of 3-chloro-1,2 propanediol were easily obtained in good yields from epichlorohydrin and alcohols under catalysis of actived montmorillonite K 10.
- Thuy, Vu Moc,Petit, Huguette,Maitte, Pierre
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p. 261 - 262
(2007/10/02)
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- The Transition Metal Catalyzed Nucleophilic Epoxide Ring Opening Reaction
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The catalytic influence of MoO2(acac)2, Mo(CO)6, MoCl5, WCl6 and TaCl5 on the reaction of 1,2-epoxy-octane with ethanol at 100 deg C in dioxan or chlorobenzene as solvents is proved.Water and hydroperoxides react with a higher rate than alcohols.When changing from primary to secondary and tertiary alcohols a decrease of the reaction rate is observed. 2,3- and 3,4-Epoxyheptane and cis- and trans-4,5-epoxy-octane react more slowly than the corresponding 1,2-epoxides.Epichlorhydrin and methylglycidether react with a lower, cyclohexene oxide, styrene oxide and norbornene oxide react with a higher rate than 1,2-epoxyoctane.The reactivities of the two dicyclopentadiene monoepoxides correspond with the reactivities of the norbornene and cyclopentene oxides.In the molybdenum catalyzed epoxide ring opening reaction an isomer distribution appears in favour of the 1-hydroxy-2-ethoxy-alkane 2.A mechanism in the coordination sphere of the transition metal complex is proposed.
- Lauterbach, G.,Posselt, G.,Schaefer, R.,Schnurpfeil, D.
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p. 101 - 120
(2007/10/02)
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