- Esterification or Thioesterification of Carboxylic Acids with Alcohols or Thiols Using Amphipathic Monolith-SO3H Resin
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We have developed a method for the esterification of carboxylic acids with alcohols using amphipathic, monolithic-resin bearing sulfonic acid moieties as cation exchange functions (monolith-SO3H). Monolith-SO3H efficiently catalyzed the esterification of aromatic and aliphatic carboxylic acids with various primary and secondary alcohols (1.55.0 equiv) in toluene at 6080 °C without the need to remove water generated during the reaction. The amphipathic property of monolith-SO3H facilitates dehydration due to its capacity for water absorption. This reaction was also applicable to thioesterification, wherein the corresponding thioesters were obtained in excellent yield using only 2.0 equiv of thiol in toluene, although heating at 120 °C was required. Moreover, monolith-SO3H was separable from the reaction mixtures by simple filtration and reused for at least five runs without decreasing the catalytic activity.
- Ichihara, Shuta,Ishida, Moeka,Ito, Ryo,Kato, Ayumu,Monguchi, Yasunari,Nakamura, Shinji,Park, Kwihwan,Sajiki, Hironao,Takada, Hitoshi,Wakayama, Fumika,Yamada, Tsuyoshi,Yamada, Yutaro
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p. 2702 - 2710
(2022/01/19)
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- Ambulation of Incipient Proton during Gas-Phase Dissociation of Protonated Alkyl Dihydrocinnamates
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Upon activation in the gas phase, protonated alkyl dihydrocinnamates undergo an alcohol loss. However, the mechanism followed is not a simple removal of an alkanol molecule after a protonation on the alkoxy group. The mass spectrum of the m/z 166 ion for deuteron-charged methyl dihydrocinnamate showed two peaks of 1:5 intensity ratio at m/z 133 and 134 to confirm that the incipient proton is mobile. The proton initially attached to the carbonyl group migrates to the ring and randomizes before a subsequent transfer of one of the ring protons to the alkoxy group for the concomitant alcohol elimination. Moreover, protonated methyl dihydrocinnamate undergoes more than one H/D exchange. The spectra recorded from m/z 167 and 168 ions obtained for di- and tri-deuterio isotopologues showed peak pairs at m/z 134, 135 and 135, 136, at 1:2 and 1:1 intensity ratios, respectively, confirming the benzenium ion intermediate achieves complete randomization before the proton transfer. Additionally, protonated higher esters of alkyl dihydrocinnamates undergo a cleavage of the O-CH2 bond to form an ion/neutral complex, which, upon activation, dissociates generating a carbenium ion and dihydrocinnamic acid, or rearranges to generate protonated dihydrocinnamic acid and an alkene by a nonspecific proton transfer.
- Xu, Sihang,Zhang, Yong,Errabelli, Ramu,Attygalle, Athula B.
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p. 9468 - 9479
(2015/10/12)
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- Sulfonated polypyrene (S-PPR) as efficient catalyst for esterification of carboxylic acids with equimolar amounts of alcohols without removing water
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Sulfonated polypyrene (S-PPR) efficiently catalyzed the reactions between carboxylic acids and equimolar amounts of alcohols with and without heptane to give the corresponding esters in good to excellent yields. Esterification was carried out at 110 °C without removing water. Transesterification of carboxylic esters with a slight excess of alcohols smoothly proceeded without heptane to give the corresponding esters in good yields. For these reactions, S-PPR was recycled without significant loss of activities.
- Tanemura, Kiyoshi,Suzuki, Tsuneo
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p. 1972 - 1975
(2013/04/23)
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- Efficient direct ester condensation between equimolar amounts of carboxylic acids and alcohols catalyzed by trifluoromethanesulfonic acid (TfOH) in Solkane365mfc
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A simple, practical, and environmentally benign esterification protocol has been devised on the basis of TfOH as the catalyst and Solkane365mfc as the reaction medium. The direct condensation of equimolar amounts of various carboxylic acids and alcohols was conveniently carried out without recourse to any additional water removal technique, giving the desired carboxylic esters in excellent yields.
- Xu, Xiu-Hua,Azuma, Ayaka,Taniguchi, Misaki,Tokunaga, Etsuko,Shibata, Norio
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p. 3848 - 3852
(2013/04/23)
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- Umpolung reactions in an ionic liquid catalyzed by electrogenerated N-heterocyclic carbenes. Synthesis of saturated esters from activated α,β-unsaturated aldehydes
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The umpolung reaction of α,β-unsaturated aldehydes to saturated esters has been carried out in an ionic liquid by organocatalysis of electrogenerated NHC. The roles of solvent, precatalyst and proton donor of the ionic liquid have been verified and good to high yields of esters have been obtained using a "green" and mild methodology.
- Feroci, Marta,Chiarotto, Isabella,Orsini, Monica,Pelagalli, Romina,Inesi, Achille
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supporting information; experimental part
p. 5361 - 5363
(2012/06/30)
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- Esterifications of carboxylic acids and alcohols catalyzed by Al 2(SO4)3 · 18H2O under solvent-free condition
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Esterifications of equimolar mixture of carboxylic acids and alcohols can be effectively catalyzed by Al2(SO4)3 · 18H2O under solvent-free condition. The esterification catalyzed by Al2(SO4)3 · 18H2O is a promising green method thanks to no need of organic solvent, no pollution, no causticity and ease to handle after reaction. This catalyst is of a low toxicity (usually it is used as purifying agent for drinking water), low-cost compound and is easily separated from the reaction mixture by simple filtration. Moreover, the catalyst can be recycled for the further esterification and the conversion does not evidently decrease.
- Gang, Li,Wenhui, Pang
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experimental part
p. 559 - 565
(2011/01/07)
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- Protic acid immobilized on solid support as an extremely efficient recyclable catalyst system for a direct and atom economical esterification of carboxylic acids with alcohols
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(Chemical Equation Presented) A convenient and clean procedure of esterification is reported by direct condensation of equimolar amounts of carboxylic acids with alcohols catalyzed by an easy to prepare catalyst system of perchloric acid immobilized on silica gel (HClO4-SiO2). The direct condensation of aryl, heteroaryl, styryl, aryl alkyl, alkyl, cycloalkyl, and long-chain aliphatic carboxylic acids with primary/secondary alkyl/cycloalkyl, allyl, propargyl, and long-chain aliphatic alcohols has been achieved to afford the corresponding esters in excellent yields. Chiral alcohol and N-t-Boc protected chiral amino acid also resulted in ester formation with the representative carboxylic acid or alcohol without competitive N-t-Boc deprotection and detrimental effect on the optical purity of the product demonstrating the mildness and chemoselectivity of the procedure. The esters of long-chain (>C10) acids and alcohols are obtained in high yields. The catalyst is recovered and recycled without significant loss of activity. The industrial application of the esterification process is demonstrated by the synthesis of prodrugs of ibuprofen and a few commercial flavoring agents. Other protic acids such as H2SO4, HBr, TfOH, HBF4, and TFA that were adsorbed on silica gel were less effective compared to HClO4-SiO2 following the order HClO4-SiO 2 ? H2SO4-SiO2 > HBr-SiO 2 > TfOH-SiO2 ? HBF4-SiO2 ≈ TFA-SiO2. When HClO4 was immobilized on other solid supports the catalytic efficiency followed the order HClO4-SiO 2 > HClO4-K10 > HClO4-Al 2O3 (neutral) > HClO4-Al2O 3 (acidic) > HClO4-Al2O3 (basic).
- Chakraborti, Asit K.,Singh, Bavneet,Chankeshwara, Sunay V.,Patel, Alpesh R.
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supporting information; experimental part
p. 5967 - 5974
(2009/12/24)
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- Mild, powerful, and robust methods for esterification, amide formation, and thioesterification between acid chlorides and alcohols, amines, thiols, respectively
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We developed two efficient practical methods for esterification, amide formation, and thioesterification between acid chlorides and alcohols, amines, thiols, respectively. The present mild and robust reaction was performed by two separate methods both by combining cheap and readily available amines, N-methylimidazole, and N,N,N′,N′-tetramethylethylenediamine (TMEDA). Method A uses catalytic N-methylimidazole and TMEDA with an equimolar amount of K2CO3, whereas Method B uses equimolar amounts of N-methylimidazole and TMEDA. The salient features are as follows. (i) With regard to reactivity, Method B was superior to Method A for esterification and thioesterification, whereas cost-effective Method A was superior to Method B for amide formation. (ii) Amide formation proceeded smoothly between acid chlorides and less nucleophilic and stereocongested amines such as 2,6-dichloroaniline. (iii) This protocol was applied to the successful synthesis of two agrochemicals, bromobutide and carpropamid.
- Nakatsuji, Hidefumi,Morimoto, Mami,Misaki, Tomonori,Tanabe, Yoo
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p. 12071 - 12080
(2008/03/13)
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- Metal bis(perfluorooctanesulfonyl)amides as highly efficient Lewis acid catalysts for fluorous biphase organic reactions
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In fluorous biphase system, metal bis(perfluorooctanesulfonyl)amides are better Lewis acid catalysts than the analogous triflates toward either transesterifications, or direct esterifications, or Friedel-Crafts acylations or Baeyer-Villiger oxidations. These catalysts are selectively soluble in lower fluorous phase and can be recovered simply by phase separation. Furthermore, these catalysts can be reused without decrease of activity in most cases.
- Hao, Xiuhua,Yoshida, Akihiro,Nishikido, Joji
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p. 193 - 199
(2007/10/03)
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- Water solvent method for esterification and amide formation between acid chlorides and alcohols promoted by combined catalytic amines: Synergy between N-methylimidazole and N,N,N′,N′-tetramethylethylenediamine (TMEDA)
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An efficient method for esterification between acid chlorides and alcohols in water as solvent has been developed by combining the catalytic amines, N-methylimidazole and N,N,N′,N′-tetramethylethylenediamine (TMEDA). The present Schotten-Baumann-type reaction was performed by maintaining the pH at around 11.5 using a pH controller to prevent the decomposition of acid chlorides and/or esters and to facilitate the condensation. The choice of catalysts (0.1 equiv.) was crucial: the combined use of N-methylimidazole and TMEDA exhibited a dramatic synergistic effect. The catalytic amines have two different roles: (i) N-methylimidazole forms highly reactive ammonium intermediates with acid chlorides and (ii) TMEDA acts as an effective HCl binder. The production of these intermediates was rationally supported by a careful 1H NMR monitoring study. Related amide formation was also achieved between acid chlorides and primary or secondary amines, including less nucleophilic or water-soluble amines such as 2-(or 4-)chloroaniline, the Weinreb N-methoxyamine, and 2,2-dimethoxyethanamine.
- Nakatsuji, Hidefumi,Morita, Jun-Ichi,Misaki, Tomonori,Tanabe, Yoo
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p. 2057 - 2062
(2007/10/03)
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- A facile, catalytic and environmentally benign method for esterification of carboxylic acids and transesterification of carboxylic esters with nearly equimolar amounts of alcohols
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A practical and green chemical process for the esterification of carboxylic acids with alcohols and transesterification of carboxylic esters in good to excellent yields by using K5CoW12O14· 3H2O (0.1 mol%) as catalyst is reported. The catalyst exhibited remarkable reusable activity. Georg Thieme Verlag Stuttgart.
- Bose, D. Subhas,Satyender, Apuri,Das, A. P. Rudra,Mereyala, Hari Babu
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p. 2392 - 2396
(2008/02/08)
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- Facile oxidative conversion of alcohols to esters using molecular iodine
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A simple, efficient, and high-yield procedure for the oxidative conversion of alcohols to various types of esters and ketones, with molecular iodine and potassium carbonate was successfully carried out.
- Mori, Naoshi,Togo, Hideo
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p. 5915 - 5925
(2007/10/03)
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- Highly efficient solvent-free condensation of carboxylic acids with alcohols catalysed by zinc perchlorate hexahydrate, Zn(ClO4) 2·6 H2O
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Zinc perchlorate hexahydrate, Zn(ClO4)2· 6 H2O, efficiently catalyses the esterification between nearly equimolar amounts of carboxylic acids and alcohols. The reaction works under solvent-free conditions at relatively low temperatures. Excellent results were obtained with a wide range of substrates.
- Bartoli,Boeglin,Bosco,Locatelli,Massaccesi,Melchiorre,Sambri
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- Recyclable and selective Lewis acid catalysts for transesterification and direct esterification in a fluorous biphase system: Tin(IV) and hafnium(IV) bis(perfluorooctanesulfonyl)amide complexes
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Tin(IV) and hafnium(IV) bis(perfluorooctanesulfonyl)amide complexes were shown to give excellent yield and selectivity for highly practical transesterification and direct esterification, respectively, with an equimolar ratio of the reactants in a fluorous biphase system. It was found that these metal complexes were completely recovered and reused in the immobilized fluorous phase without loss of their catalytic activities.
- Hao, Xiuhua,Yoshida, Akihiro,Nishikido, Joji
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p. 781 - 785
(2007/10/03)
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- 4-(Nitro)-diphenylammonium triflate(NDPAT) catalysed esterification of carboxylic acids with alcohols
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4-(Nitro)-diphenylammonium triflate(NDPAT) efficiently catalysed the esterification between equimolar amounts of carboxylic acids and alcohols in good yield under mild reaction conditions.
- Liu, Xuan-Gan,Hu, Wei-Xiao
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p. 564 - 565
(2007/10/03)
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- Novel and efficient method for esterification, amidation between carboxylic acids and equimolar amounts of alcohols, and amines utilizing Me2NSO2Cl and N,N-dimethylamines; Its application to the synthesis of coumaperine, a natural chemopreventive dieneamide
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Various carboxylic esters or amides were prepared in good to excellent yield between carboxylic acids and equimolar amounts of alcohols or amines under very mild conditions (0-45°C; within 3 h) using dimethylsulfamoyl chloride (Me2NSO2Cl; 1) combined with N,N-dimethylamines (Me2NR: 2a; R=Me, 2b; R=Bu). The choice of the sulfamoyl chloride and the amine is crucial for the reaction; that is, sterically uncrowded amines accelerated the present esterification and amidation. This agent had some advantages over methanesulfonyl chloride (3)/amines as for the atom-economy, avoidance of side reactions, and had very high chemoselectivity toward the carboxyl group vs the hydroxyl group; the experiment was performed by the addition of 1 to the mixture of carboxylic acids and alcohols. Application of this method to the synthesis of coumaperine, a chemopreventive natural product, was performed using the present amidation as a key step.
- Wakasugi, Kazunori,Nakamura, Atsushi,Iida, Akira,Nishii, Yoshinori,Nakatani, Nobuji,Fukushima, Shoji,Tanabe, Yoo
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p. 5337 - 5345
(2007/10/03)
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- Simple, Mild, and Practical Esterification, Thioesterification, and Amide Formation Utilizing p-Toluenesulfonyl Chloride and N-Methylimidazole
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We have developed an efficient method for the esterification or thioesterification of equimolar amounts of carboxylic acids and alcohols or thiols using a novel reagent, p-toluenesulfonyl chloride (TsCl) together with N-methylimidazole. The present method is simple, mild, and reactive, uses readily available and economical reagents. The choice of amine is critical for the present method. The amine, N-methylimidazole, has two roles: (i) as an HCl scavenger for the initial smooth generation of mixed anhydrides between carboxylic acids and TsCl and (ii) successive formation of highly reactive ammonium intermediates from mixed anhydrides. This method could be applied to various types of carboxylic acids, alcohols, and thiols: a) several functionalities were tolerated; b) two N-Cbz amino acids were smoothly esterified without racemization; and c) the labile 1β-methylcarbapenem key intermediate and a pyrethroid insecticide, prallethrin, were successfully prepared. The related amide formation between carboxylic acids and primary or secondary amines was also performed. The proposed reaction mechanism involves a novel method for producing the reactive acylammonium intermediates. The production of these intermediates was rationally supported by a careful 1H NMR monitoring study.
- Wakasugi, Kazunori,Iida, Akira,Misaki, Tomonori,Nishii, Yoshinori,Tanabe, Yoo
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p. 1209 - 1214
(2007/10/03)
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- Fluoroalkyldistannoxane Catalysts for Transesterification in Fluorous Biphase Technology
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Novel, practical protocols of transesterification have been advanced with recourse to fluorous biphase technology. The fluoroalkyldistannoxane catalysts enable transesterification in FC-72 solvent to furnish 100% yields of the desired esters by use of reactants ester and alcohol in a 1:1 ratio. The catalysts also work in FC-72/organic solvent system as well as in toluene alone. A number of esters and alcohols bearing various functional groups are employable. The catalysts can be totally recovered and reused. More conveniently, the catalyst solution in FC-72 which is separated from the reaction mixture is directly used for the next reaction.
- Xiang, Jiannan,Orita, Akihiro,Otera, Junzo
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- Fluorous biphasic esterification directed towards ultimate atom efficiency
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Aperfectly selective esterification that discriminates between primary and sterically hindered or aromatic carboxylic acids occurs in the presence of the fluoroalkyldistannoxane [{Cl(C6F13CH2 CH2)2SnOSn(CH2CH2 -C6F13)2Cl}2] (1). The reaction gives 100% yield with a strict 1:1 ratio of the carboxylic acid and alcohol reactants, and the catalyst can be recycled without any loss of activity.
- Xiang, Jiannan,Orita, Akihiro,Otera, Junzo
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p. 4117 - 4119
(2007/10/03)
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- A practical and green chemical process: Fluoroalkyldistannoxane-catalyzed biphasic transesterification
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There is no need for the recovery of the catalyst in the fluorous biphasic transesterification catalyzed by [{Cl(C6F13CH2CH2)2 SnOSn(C6F13CH2CH2) 2Cl}2] (1; see scheme), which results in quantitative conversions and yields. An FC-72 solution of the dimeric flouroalkyldistannoxane 1 can be recycled repeatedly without having to recover the neat catalyst.
- Xiang, Jiannan,Toyoshima, Shinji,Orita, Akihiro,Otera, Junzo
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p. 3670 - 3672
(2007/10/03)
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- Me2NSO2Cl and N,N-dimethylamines; a novel and efficient agent for esterification, amidation between carboxylic acids, and equimolar amounts of alcohols and amines
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Various carboxylic esters or amides were prepared in good to excellent yields between carboxylic acids and equimolar amounts of alcohols or amines under very mild conditions using dimethylsulfamoyl chloride (Me2NSO2Cl) combined with N,N-dimethylamines. The choice of the sulfamoyl chloride and the amine is crucial for the reactions.
- Wakasugi, Kazunori,Nakamura, Atsushi,Tanabe, Yoo
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p. 7427 - 7430
(2007/10/03)
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- Diphenylammonium triflate (DPAT): Efficient catalyst for esterification of carboxylic acids and for transesterification of carboxylic esters with nearly equimolar amounts of alcohols
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Diphenylammonium triflate (DPAT) efficiently catalyzed esterification between equimolar amounts of carboxylic acids and alcohols in good to excellent yields under mild reaction conditions. Transesterification of carboxylic esters with a slight excess of alcohols also proceeded using DPAT as catalyst with TMSCl as a co-catalyst. (C) 2000 Elsevier Science Ltd.
- Wakasugi, Kazunori,Misaki, Tomonori,Yamada, Kayo,Tanabe, Yoo
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p. 5249 - 5252
(2007/10/03)
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- A Novel Transesterification of Thioesters with Alcohols by an Electrochemical Activation
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Esters were synthesized from thioesters and alcohols in high yields by an electrochemical activation.Different results were obtained by the use of n-Bu4N+ I- and LiBF4 as the electrolyte.
- Yamaguchi, Masahiko,Tsukamoto, Yukiharu,Minami, Toru
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p. 1223 - 1226
(2007/10/02)
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