- Membrane transport inspired hydrolysis of non-activated esters at near physiological pH
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A positively charged micelle loaded with substrates was transported selectively to the reaction site (cathode) to promote the proximity and localization of the reactants (ester and hydroxide). The guided vehicular delivery coupled with electrolysis allows the hydrolysis of non-activated esters at near physiological pH with significant yields along with recyclability.
- Mandal, Raki,Mahanty, Kingshuk,Mandal, Subhendu,De Sarkar, Suman,Tarafdar, Pradip K.
-
supporting information
p. 11088 - 11091
(2021/10/30)
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- KMnO4-catalyzed chemoselective deprotection of acetate and controllable deacetylation-oxidation in one pot
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A novel and efficient protocol for chemoselective deacetylation under ambient conditions was developed using catalytic KMnO4. The stoichiometric use of KMnO4 highlighted the dual role of a heterogeneous oxidant enabling direct access to aromatic aldehydes in one-pot sequential deacetylation-oxidation. The reaction employed an alternative solvent system and allowed the clean transformation of benzyl acetate to sensitive aldehyde in a single step while preventing over-oxidation to acids. Use of inexpensive and readily accessible KMnO4 as an environmentally benign reagent and the ease of the reaction operation were particularly attractive, and enabled the controlled oxidation and facile cleavage of acetate in a preceding step. This journal is
- Gurawa, Aakanksha,Kumar, Manoj,Rao, Dodla S.,Kashyap, Sudhir
-
supporting information
p. 16702 - 16707
(2020/10/27)
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- Synthesis of task-specific imidazolium ionic liquid as an efficient catalyst in acetylation of alcohols, phenols, and amines
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Herein, we report the synthesis of task-specific amino-functionalized imidazolium ionic liquid, acetate1-(2-tert-butoxycarbonylamino-ethyl)-3-methyl-3H-imidazol-1-ium; (Boc-NH-EMIM.OAc), as an efficient catalyst for the acetylation of alcohols, phenols, and amines in the presence of acetic anhydride (acetylating reagent). Remarkably, acetic anhydride in the presence of 10?molpercent of catalyst (Boc-NH-EMIM.OAc) under solvent-free conditions showed excellent acetylation activity in shorter duration of time. On the basis of this, a general procedure for acetylation of alcohols, phenols, and amines has been developed. The ionic liquid (Boc-NH-EMIM.OAc) can be readily recovered and reused successfully up to four consecutive cycles without any significant loss of its catalytic activity. We have been able to show that this acetylating method has many advantages. It gives high yields, takes shorter time, and develops the possibility of benign environmental-friendly process.
- Chaubey, Snehkrishn A.,Mishra, Roli
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p. 3259 - 3268
(2020/04/17)
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- Coating of polydopamine on polyurethane open cell foams to design soft structured supports for molecular catalysts
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Polydopamine-coated polyurethane open cell foams are used as structured supports for molecular catalysts through the covalent anchoring of alkoxysilyl arms by the catechol groups of the mussel-inspired layer. This strong bonding prevents their leaching. No alteration of the mechanical properties of the flexible support is observed after repeated uses of the catalytic materials.
- Ait Khouya, Ahmed,Mendez Martinez, Miguel L.,Bertani, Philippe,Romero, Thierry,Favier, Damien,Roland, Thierry,Guidal, Valentin,Bellière-Baca, Virginie,Edouard, David,Jierry, Lo?c,Ritleng, Vincent
-
supporting information
p. 11960 - 11963
(2019/10/11)
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- Atom- and Step-Economical Ruthenium-Catalyzed Synthesis of Esters from Aldehydes or Ketones and Carboxylic Acids
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We developed a ruthenium-catalyzed reductive ester synthesis from aldehydes or ketones and carboxylic acids using carbon monoxide as a deoxygenative agent. Multiple factors influencing the outcome of the reaction were investigated. Best results were obtained for commercially available and inexpensive benzene ruthenium chloride; as low as 0.5 mol % of the catalyst is sufficient for efficient reaction. Competitive studies demonstrated that the presence of even 1000 equiv of alcohol in the reaction mixture does not lead to the corresponding ester, which clearly indicates that the process is not a simple reductive esterification but a novel type of Ru-catalyzed redox process.
- Runikhina, Sofiya A.,Usanov, Dmitry L.,Chizhov, Alexander O.,Chusov, Denis
-
supporting information
p. 7856 - 7859
(2019/01/14)
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- Efficient O-Acylation of Alcohols and Phenol Using Cp2TiCl as a Reaction Promoter
-
A method has been developed for the conversion of primary, secondary, and tertiary alcohols, and phenol, into the corresponding esters at room temperature. The method uses a titanium(III) species generated from a substoichiometric amount of titanocene dichloride together with manganese(0) as a reductant, as well as methylene diiodide. It involves a transesterification from an ethyl ester, or a reaction with an acyl chloride. A radical mechanism is proposed for these transformations.
- Durán-Pe?a, María Jesús,Botubol-Ares, José Manuel,Hanson, James R.,Hernández-Galán, Rosario,Collado, Isidro G.
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supporting information
p. 3584 - 3591
(2016/07/28)
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- Synthesis and characterization of ionic liquid immobilized on magnetic nanoparticles: A recyclable heterogeneous organocatalyst for the acetylation of alcohols
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Herein, we describe a simple and efficient procedure for the preparation of 3-((3-(trisilyloxy)propyl)propionamide)-1-methylimidazolium chloride ionic liquid supported on magnetic nanoparticle (TPPA-IL-Fe3O4). The structure of this magnetic ionic liquid is fully characterized by FT-IR, TGA, XRD, VSM, SEM, EDX and DLS techniques. TPPA-IL-Fe3O4 is employed as a catalyst for the acetylation of alcohols with acetic anhydride under mild and heterogeneous conditions at room temperature with good to excellent yields. The magnetic catalyst could be readily separate from the reaction media by simple magnetic decantation, and reused several times without significant loss of its catalytic activity.
- Ghorbani-Choghamarani, Arash,Norouzi, Masoomeh
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p. 832 - 840
(2015/11/16)
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- Tribromo melamine as novel and versatile catalyst for the formylation and acetylation of alcohols
-
Tribromo melamine has been found to be an efficient and green organocatalyst for the acetylation and formylation reactions of alcohols with acetic anhydride and ethyl formate at room temperature and under mild reaction conditions.
- Hajjami, Maryam,Ghorbani-Choghamarani, Arash,Karamshahi, Zahra,Norouzi, Masoomeh
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p. 260 - 263
(2014/03/21)
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- ZnAl2O4@SiO2 nanocomposite catalyst for the acetylation of alcohols, phenols and amines with acetic anhydride under solvent-free conditions
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A ZnAl2O4@SiO2 nanocomposite was prepared from metal nitrates and tetraethyl orthosilicate by the sol-gel process, and characterized by X-ray diffraction, Fourier transform infrared, transmission electron microscopy, and N2 adsorption-desorption measurements. The nanocomposite was tested as a heterogeneous catalyst for the acetylation of alcohols, phenols, and amines under solvent-free conditions. Under optimized conditions, efficient acetylation of these substrates with acetic anhydride over the ZnAl2O4@SiO2 nanocomposite was obtained. Acetylation of anilines and primary aliphatic amines proceeded rapidly at room temperature, while the reaction time was longer for the acetylation of alcohols and phenols, showing that an amine NH2 group can be selectively acetylated in the presence of alcoholic or phenolic OH groups. The catalyst can be reused without obvious loss of catalytic activity. The catalytic activity of the ZnAl2O4@SiO2 nanocomposite was higher than that of pure ZnAl2O4. The method gives high yields, and is clean, cost effective, compatible with substrates having other functional groups and it is suitable for practical organic synthesis.
- Farhadi, Saeed,Jahanara, Kosar
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p. 368 - 375
(2014/04/03)
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- Sol-gel derived LaFeO3/SiO2 nanocomposite: Synthesis, characterization and its application as a new, green and recoverable heterogeneous catalyst for the efficient acetylation of amines, alcohols and phenols
-
LaFeO3/SiO2 nanocomposite was synthesized by the sol-gel process from metal nitrates and tetraethyl orthosilicate (TEOS) as the SiO2 source. The nanocomposite product was characterized by XRD, FT-IR, SEM, and surface area measurements and was used as a heterogeneous catalyst for the efficient acetylation of amines, alcohols and phenols to the corresponding acetates using acetic anhydride under solvent-free conditions. Among the various substrates, acetylation of amines was preceded rapidly, so that an amine group could be selectively acetylated in the presence of alcoholic or phenolic hydroxyl groups by the appropriate choice of reaction time. The catalyst can also be reused several times without the loss of activity. In addition, the catalytic activity of the LaFeO3/SiO2 nanocomposite was higher than that of the pure LaFeO3 nanoparticles. The method is high yielding, clean, cost effective, compatible with the substrates having other functional groups and very suitable for the practical organic synthesis.
- Farhadi, Saeed,Jahanara, Kosar,Sepahdar, Asma
-
p. 1103 - 1112
(2014/08/05)
-
- L-pyrrolidine-2-carboxylic acid-4-hydrogen sulfate (supported on silica gel) as a new and efficient catalyst for acylation of alcohols, phenols and amines under solvent-free conditions
-
In the present work, L-pyrrolidine-2-carboxylic acid-4-hydrogen sulfate, supported on silica gel was prepared and characterized by Mass spectroscopy, 1H NMR, 13CNMR, FT IR and elemental analysis (CHN) methods. This heterogenized catalyst can be used as an efficient catalyst for the acylation of alcohols, phenols, and amines with acetic anhydride under mild and solvent-free conditions. Simple work-up, stability of the catalyst, nontoxicity and good to high yields are the advantages of this work.
- Hajjami, Maryam,Ghorbani-Choghamarani, Arash,Khani, Zahra
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p. 324 - 329
(2013/07/26)
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- Acetylation of alcohols with acetic anhydride promoted by N,N,N-trimethylanilinium tribromide
-
A wide variety of alcohols were reacted with acetic anhydride at room temperature in the presence of a catalytic amount of N,N,N-trimethylanilinium tribromide to produce the corresponding alkyl acetates in good to excellent yields. Following this procedure, acetylation of primary, secondary, and tertiary alcohols has been performed under neutral conditions.
- Ghorbani-Choghamarani,Shiri,Rostami
-
p. 1728 - 1730
(2014/08/05)
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- A lewis acid-promoted pinner reaction
-
Carbonitriles and alcohols react in a Lewis acid-promoted Pinner reaction to carboxylic esters. Best results are obtained with two equivalents of trimethylsilyl triflate as Lewis acid. Good yields are achieved with primary alcohols and aliphatic or benzylic carbonitriles, but the straightforward synthesis of acrylates and benzoates starting with acrylonitrile and benzonitrile, respectively, is similarly possible. Phenols are not acylated under these reaction conditions. The method has been used for the first total synthesis of the natural product monaspilosin. In the reaction of benzyl alcohols variable amounts of amides are formed in a Ritter-type side reaction.
- Pfaff, Dominik,Nemecek, Gregor,Podlech, Joachim
-
supporting information
p. 1572 - 1577
(2013/10/22)
-
- Role of water and p-fluorobenzoic acid in mn(ii)t(p-cl)pp catalyzed aerobic oxidation of p-fluorotoluene
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A solvent-free manganoporphyrin-catalyzed oxidiation of p-fluorotoluene was developed, using oxygen as a clean and cheap oxidant. The parameters that have relationship with conversion were investigated. The conversion of p-fluorotoluene was found to be depend on the stability of catalytic environment. Water and p-fluorobenzoic acid were the final oxidation products of p-fluorotoluene, would inhibit the activity of catalyst. The conversion would be increased from 7.0 to 16.5 %, by the dehydration of acetic anhydride.
- Fang, Yong-Qi,Lv, Chun-Xu,Lu, Ming
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p. 313 - 315
(2013/02/22)
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- Polyvinylpolypyrrolidone-bound boron trifluoride: A highly efficient catalyst for acylation of alcohols, phenols and trimethylsilyl ethers by acetic anhydride
-
A highly efficient method for the acylation of alcohols, phenols and trimethylsilyl ethers with acetic anhydride is described using polyvinylpolypyrrolidone-bound boron trifluoride (PVPP-BF3) under mild and heterogeneous conditions at room temperature in good to excellent yields. The polyvinylpolypyrrolidone-boron trifluoride complex shows more water tolerant, non-corrosive and stable solid catalyst elevated Lewis acid properties.
- Mokhtary, Masoud,Qandalee, Mohammad,Najafizadeh, Faranak
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experimental part
p. 389 - 393
(2012/08/28)
-
- Solvent-free transesterification in a ball-mill over alumina surface
-
An efficient procedure for transesterification has been developed in a ball-mill in the absence of any solvent, acid/base or metal catalyst. A variety of methyl, ethyl, allyl esters have been transesterified to higher benzyl and other esters in high yields by this procedure.
- Chatterjee, Tanmay,Saha, Debasree,Ranu, Brindaban C.
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experimental part
p. 4142 - 4144
(2012/08/28)
-
- Spinel-type zinc aluminate (ZnAl2O4) nanoparticles prepared by the co-precipitation method: A novel, green and recyclable heterogeneous catalyst for the acetylation of amines, alcohols and phenols under solvent-free conditions
-
Zinc aluminate (ZnAl2O4) nanoparticles with an average particle size of about 8 nm were easily prepared by the co-precipitation method using aqueous ammonia solution as the precipitating agent. This nanosized spinel-type oxide was characterized by TGA, XRD, FT-IR, TEM, and surface area measurement and used as the heterogeneous catalyst for the acetylation reaction. Efficient acetylation of various amines, alcohols and phenols was carried out over ZnAl2O4 nanoparticles using acetic anhydride and/or acetyl chloride as the acetylating agents at room temperature without the use of a solvent. The method is highly selective, allowing the alcoholic hydroxyl group to be protected while the phenolic hydroxyl group remains intact, and the amine group can be acetylated in the presence of the hydroxyl group. This method is fast and has a high yield. It is also clean, safe, cost effective, compatible with substrates that have other functional groups and very suitable for practical organic synthesis. In addition, the catalyst can be reused without significant loss of activity. Indeed, the catalytic activity of the ZnAl2O4 nanoparticles is higher than that of bulk ZnAl2O4.
- Farhadi, Saeid,Panahandehjoo, Somayeh
-
scheme or table
p. 293 - 302
(2010/09/04)
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- Trialkylsilyl triflimides as easily tunable organocatalysts for allylation and benzylation of silyl carbon nucleophiles with non-genotoxic reagents
-
Trialkylsilyl triflimides generated in situ are unique catalysts for the electrophilic benzylation or allylation of trialkylsilylenol ethers or allyl trialkylsilanes with non-genotoxic alkylating reagents such as benzyl and allyl acetates. In most cases the reactions are fast at room temperature and yields are high. The reaction works particularly well with electron-rich benzyl donors including derivatives of pyrrole, indole and furane.
- Mendoza, Oscar,Rossey, Guy,Ghosez, Léon
-
supporting information; experimental part
p. 2571 - 2575
(2010/06/21)
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- P-Toluenesulfonyl chloride as a new and effective catalyst for acetylation and formylation of hydroxyl compounds under mild conditions
-
The catalytic application of p-toluenesulfonyl chloride for efficient acetylation of various types of alcohols and phenols with acetic anhydride in solvent-free conditions is reported. Also structurally diverse alcohols were formylated using formic acid based on the use of catalytic amount of p-toluenesulfonyl chloride under solvent-free condition. The reactions were carried out in short reaction time and in good to excellent yields at room temperature.
- Khazaei, Ardeshir,Rostami, Amin,Mantashlo, Fatemeh
-
experimental part
p. 1430 - 1434
(2011/10/08)
-
- Thallium(III) chloride: A mild and efficient catalyst for acylation of alcohols, phenols and thiols, and for geminal diacylation of aldehydes under solvent-free conditions
-
Thallium(III) chloride is a simple and efficient catalyst for acylation of alcohols, phenols and thiols. It is also very effective for geminal diacylation of aldehydes. The acylation reaction using acetic anhydride proceeds in excellent yield in the presence of catalytic amounts of thallium(III) chloride (1 mol%) at room temperature within relatively short reaction times (20 min). Structurally diverse alcohols, phenols, thiols and aldehydes undergo acylation under solvent-free conditions.
- Kadam, Santosh T.,Kim, Sung Soo
-
experimental part
p. 3307 - 3313
(2009/05/07)
-
- Phosphomolybdic acid: Mild and efficient catalyst for acetylation of alcohols, phenols, and amines under solvent-free conditions
-
Phosphomolybdic acid (PMA) has been found to be a simple and efficient catalyst for the acetylation of alcohols, phenols, and amines. Acetylation reactions with acetic anhydride (1.0 equiv) proceed in excellent yield in the presence of a catalytic amount (0.2 mol%) of PMA at ambient temperature within a relatively short reaction time (10 min). Structurally diverse alcohols, phenols, and amines undergo acetylation under solvent-free conditions. Georg Thieme Verlag Stuttgart.
- Kadam, Santosh T.,Sung, Soo Kim
-
p. 267 - 271
(2008/12/22)
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- Transformations of para-substituted benzylcyclopropanes, allylbenzenes, and diphenylmethanes under nitration with nitric acid in acetic anhydride
-
Electrophilic nitration of benzylcyclopropanes, allylbenzenes, and diphenylmethanes containing ortho, para-orienting substituents in the para position of the benzene ring results mainly in replacement of the cyclopropylmethyl, allyl, or benzyl group, respectively (ipso substitution). The nitration of 4-cyclopropylallylbenzene is not accompanied by nitrodealkylation, and the products are only 2- and 3-nitro-4-cyclopropylallylbenzenes.
- Mochalov,Gazzaeva,Fedotov,Archegov,Trofimova,Shabarov,Zefirov
-
p. 406 - 416
(2007/10/03)
-
- An amino alcohol ligand for highly enantioselective addition of organozinc reagents to aldehydes: Serendipity rules
-
(matrix presented) Amino alcohol 4 (or its enantiomer) is prepared in two simple steps. Commercial (1R,2S)-2-amino-1,2-diphenylethanol is dialkylated with bis(2-bromoethyl) ether. Subsequent hydrogenation over 5% Rh on alumina in the presence of morpholine unexpectedly stops at the hexahydro derivative 4. Amino alcohol 4 promotes the enantioselective addition of diethylzinc to aldehydes at room temperature in up to 99% enantiomeric excess.
- Nugent, William A.
-
p. 2133 - 2136
(2007/10/03)
-
- Electroreductive Acylation of Benzyl Chlorides with Acid Anhydrides. Stereoselective Formation of (E)-Enol Esters from Benzyl Alkyl Ketones
-
Electroreduction of benzyl chlorides in the presence of acid anhydrides brought about stereoselective formation of (E)-enol esters of the corresponding benzyl alkyl ketones, the initial acylated products, in good to moderate yields.
- Nishiguchi, Ikuzo,Oki, Tsuneo,Hirashima, Tsuneaki,Shiokawa, Jiro
-
p. 2005 - 2008
(2007/10/02)
-
- SUBSTITUENT EFFECTS IN THE PHOTOSOLVOLYSIS OF BENZYL DERIVATIVES. GENERAL STRUCTURE-REACTIVITY RELATIONSHIPS.
-
The relative reactivity of photosolvolysis of a number of substituted benzyl acetates is in the order ortho > meta > para, these substitutent effects being apparently additive, as suggested by the relative reactivity of photomethanolysis of several dimethoxy-susbstituted benzyl alcohols.
- Wan, Peter,Chak, Becky,Li, Carrier
-
p. 2937 - 2940
(2007/10/02)
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- (17)O NMR SPECTROSCOPY: UNUSUAL SUBSTITUENT EFFECTS IN para-SUBSTITUTED BENZYL ALCOHOLS AND ACETATES
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The (17)O chemical shifts for para-substituted benzyl alcohols and acetates were measured: electron donating substituents resulted in deshielding and electron withdrawing groups resulted in shielding of the chemical shift; the data are correlated by DSP treatment.
- Balakrishnan, P.,Baumstark, A. L.,Boykin, D. W.
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p. 169 - 172
(2007/10/02)
-
- Metal Ion Oxidation. VII. Oxidation of Aromatic Hydrocarbons by Potassium 12-Wolframocobalt(III)ate, a "Soluble Anode"
-
The oxidation of aromatic compounds with potassium 12-wolframocobalt(II)ate in acetic acid media has been investigated.A wide range of alkylaromatics can be acetoxylated in the α position, whereas nuclear substitution can be effected in the presence of acetate ion.In a few cases acetoxymethylation is observed, presumably via intermediate arylacetic acid. 4-Fluoroanisole is converted to 4-acetoxyanisole.In all preparative aspects, the reaction is closely similar to anodic and Ag(II) mediated acetoxylation.A study of substituted effects upon α acetoxylation showed a good linear relationship between log krel and Eo for oxidation of the alkylaromatic substrates (slope -3.2 V-1).A strong deuterium isotope effect (KH/kD ca. 6) is indicative of a rate-determining step involving hydrogen atom transfer ("concerted electron/proton transfer") from the α C-H bond to an oxygen of the heteropoly ion.
- Eberson, Lennart,Wistrand, Lars-Goeran
-
p. 349 - 358
(2007/10/02)
-