- Lipase-catalyzed esterification in water enabled by nanomicelles. Applications to 1-pot multi-step sequences
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Esterification in an aqueous micellar medium is catalyzed by a commercially available lipase in the absence of any co-factors. The presence of only 2 wt% designer surfactant, TPGS-750-M, assists in a 100% selective enzymatic process in which only primary alcohols participate (in a 1?:?1 ratio with carboxylic acid). An unexpected finding is also disclosed where the simple additive, PhCF3 (1 equiv. vs. substrate), appears to significantly extend the scope of usable acid/alcohol combinations. Taken together, several chemo- and bio-catalyzed 1-pot, multi-step reactions can now be performed in water.
- Akkachairin, Bhornrawin,Akporji, Nnamdi,Cortes-Clerget, Margery,Dussart-Gautheret, Jade,Gallou, Fabrice,Lipshutz, Bruce H.,Singhania, Vani,Yu, Julie
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p. 1440 - 1445
(2022/02/14)
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- Manganese-catalyzed homogeneous hydrogenation of ketones and conjugate reduction of α,β-unsaturated carboxylic acid derivatives: A chemoselective, robust, and phosphine-free in situ-protocol
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We communicate a user-friendly and glove-box-free catalytic protocol for the manganese-catalyzed hydrogenation of ketones and conjugated C[dbnd]C[sbnd]bonds of esters and nitriles. The respective catalyst is readily assembled in situ from the privileged [Mn(CO)5Br] precursor and cheap 2-picolylamine. The catalytic transformations were performed in the presence of t-BuOK whereby the corresponding hydrogenation products were obtained in good to excellent yields. The described system offers a brisk and atom-efficient access to both secondary alcohols and saturated esters avoiding the use of oxygen-sensitive and expensive phosphine-based ligands.
- Topf, Christoph,Vielhaber, Thomas
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- 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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- Development of a triazinedione-based dehydrative condensing reagent containing 4-(dimethylamino)pyridine as an acyl transfer catalyst
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A new triazinedione-based reagent, (N,N′-dialkyl)triazinedione-4-(dimethylamino)pyridine (ATD-DMAP) was developed for the operationally simple dehydrative condensation of carboxylic acids. This reagent comprises an ATD core and DMAP as the leaving group, which is liberated into the reaction system to accelerate acyl transfer reactions. Upon adding ATD-DMAP to a mixture of carboxylic acids and alcohols in the presence of an amine base, the corresponding esters were formed rapidly at room temperature. Moreover, dehydrative condensation between carboxylic acids and amines using ATD-DMAP proceeded in high yield.
- Liu, Jie,Fujita, Hikaru,Kitamura, Masanori,Shimada, Daichi,Kunishima, Munetaka
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supporting information
p. 4712 - 4719
(2021/06/11)
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- Method for selective reduction α, β - unsaturated carbonyl compound carbon-carbon double bond (by machine translation)
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The invention discloses a method for selectively reducing carbon-carbon double bonds in α and β - unsaturated carbonyl compounds, which comprises the following steps of adding α, β - unsaturated carbonyl compounds shown in formula (I) in an electrolysis system and reducing α and β - unsaturated carbonyl compounds with carbonyl-conjugated carbon-carbon double bonds through an electrochemical cathodic reduction reaction. Compared with the reported method, the method disclosed by the invention does not use a metal catalyst and an external oxidant; and the reaction raw material and the electrolyte are low in price, nontoxic and tasteless, simple and convenient in post-treatment. (by machine translation)
- -
-
Paragraph 0079-0082
(2020/06/17)
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- Oxidative Decarboxylation Enables Chemoselective, Racemization-Free Esterification: Coupling of α-Ketoacids and Alcohols Mediated by Hypervalent Iodine(III)
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An α-ketoacid could be converted into a reactive acylating agent by treatment with hypervalent iodine(III) species, and in so doing, we discovered a novel decarboxylative acylation of alcohols that affords a variety of esters in excellent yields. The esterification has been applied to a sterol bearing a free carboxylic acid and shows unique chemoselectivity. The procedure is racemization-free and operates under mild conditions.
- Nanjo, Takeshi,Kato, Natsuki,Takemoto, Yoshiji
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supporting information
p. 5766 - 5769
(2018/09/12)
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- Broadly Applicable Ytterbium-Catalyzed Esterification, Hydrolysis, and Amidation of Imides
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An efficient, broadly applicable, operationally simple, and divergent process for the transformation of imides into a range of carboxylic acid derivatives under mild conditions is reported. By simply using catalytic amounts of ytterbium(III) triflate as a Lewis acid promoter in the presence of alcohols, water, amines, or N,O-dimethylhydroxylamine, a broad range of imides is smoothly and readily converted to the corresponding esters, carboxylic acids, amides, and Weinreb amides in good yields. This method notably enables an easy cleavage of oxazolidinone-based auxiliaries.
- Guissart, Céline,Barros, Andre,Rosa Barata, Luis,Evano, Gwilherm
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supporting information
p. 5098 - 5102
(2018/09/13)
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- Development of triazine-based esterifying reagents containing pyridines as a nucleophilic catalyst
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We have developed new triazine-based esterifying reagents comprising pyridines that can act as a nucleophilic catalyst. 1-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-3,5-lutidinium chloride (DMT-3,5-LUT) was found to exhibit a superior reactivity for the dehydrating condensation reaction between carboxylic acids and alcohols. The reaction of DMT-3,5-LUT with carboxylic acids produces intermediacy of acyloxytriazines, which is known to exhibit moderate reactivity toward alcohols, with concomitant liberation of 3,5-lutidine. The subsequent chemical transformation of the acyloxytriazines and alcohols into esters can be accelerated by the action of 3,5-lutidine as a nucleophilic catalyst. The detailed reaction mechanism revealed by a time-course analysis of the reactions is also discussed.
- Yamada, Kohei,Liu, Jie,Kunishima, Munetaka
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supporting information
p. 6569 - 6575
(2018/09/25)
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- Structure–activity relations of rosmarinic acid derivatives for the amyloid β aggregation inhibition and antioxidant properties
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Amyloid-β aggregation inhibitors are expected to be therapeutic or prophylactic agents for Alzheimer's disease. Rosmarinic acid, which is one of the main aggregation inhibitors derived from Lamiaceae, was employed as a lead compound and its 25 derivatives were synthesized. In this study, the structure–activity relations of rosmarinic acid derivatives for the amyloid-β aggregation inhibitory effect (MSHTS assay), antioxidant properties, and xanthine oxidase inhibition were evaluated. Among the tested compounds, compounds 16d and 19 were found to the most potent amyloid aggregation inhibitors. The SAR revealed that the necessity of the presence of the phenolic hydroxyl on one side of the molecule as well as the lipophilicity of the entire molecule. The importance of these structural properties was also supported by docking simulations.
- Taguchi, Riho,Hatayama, Koki,Takahashi, Tomohito,Hayashi, Takafumi,Sato, Yuki,Sato, Daisuke,Ohta, Kiminori,Nakano, Hiroto,Seki, Chigusa,Endo, Yasuyuki,Tokuraku, Kiyotaka,Uwai, Koji
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supporting information
p. 1066 - 1075
(2017/08/02)
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- Hydroesterification of alkenes with sodium formate and alcohols promoted by cooperative catalysis of Ru3(CO)12 and 2-pyridinemethanol
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(Figure Presented) A chelation-assisted hydroesterification reaction of alkenes with sodium formate and alcohols that involves cooperative catalysis by Ru3(CO)12 and 2-pyridinemethanol is described. In this three-component coupling reaction, sodium formate serves as the carbon monoxide source.
- Kim, Dong-Su,Park, Woo-Jin,Lee, Chang-Hee,Jun, Chul-Ho
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p. 12191 - 12196
(2015/01/09)
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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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- One-pot sequential synthesis of ethers from an aliphatic carboxylic acid and an alcohol by indium-catalyzed deoxygenation of an ester
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We have developed a widely applicable and direct method of etherification from a carboxylic acid and an alcohol by indium-catalyzed deoxygenation of the transient ester formed in a one-pot reaction. This simple catalytic reducing system appears to be remarkably tolerant of several functional groups including alkenes, halogens, nitro and heterocyclic groups. A reducing system composed of InBr3 and an economical hydrosiloxane, PMHS (polymethylhydrosiloxane) , enabled one-pot etherification by using a variety of aliphatic carboxylic acids and alcohols. Copyright
- Sakai, Norio,Usui, Yuta,Moriya, Toshimitsu,Ikeda, Reiko,Konakahara, Takeo
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p. 4603 - 4608
(2012/10/30)
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- Exceptionally high decarboxylation rate of a primary aliphatic acyloxy radical determined by radical product yield analysis and quantitative 1H-CIDNP spectroscopy
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Symmetrical (RCO2CO2R; R=XCH2CH 2) and asymmetrical (RCO2CO2R′; R=C 9H19CH2CH2, R′=CH3 or m-ClC6H4) primary diacyl peroxides were thermally decomposed under different conditions to analyze the decarboxylation rates of the thermally generated acyloxy radicals. Quantitative models of the geminate product yields, and qualitative and quantitative 1H-CIDNP spectroscopy were used to obtain the decarboxylation rate estimates. Results reported here suggest that, unlike short chain acyloxy radicals such as propanoyloxyl, long chain acyloxy radicals possess the highest decarboxylation rates of all known acyloxy radicals, estimated at (0.5-1.5)× 10 12s-1 between 80 and 140°C. Given the nature of the dissociative state of acyloxy radicals, such rates appear to be the result of destabilization of the former by the steric bulk of the long chain substituents. Additionally, the rate of this order of magnitude suggests a nearly concerted decarboxylation of primary diacyl peroxides. Copyright
- Fraind, Alicia,Turncliff, Ryan,Fox, Teri,Sodano, Justin,Ryzhkov, Lev R.
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scheme or table
p. 809 - 820
(2012/06/29)
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- Syntheses and reactivities of non-symmetrical "active ester" bi-dentate cross-linking reagents having a phthalimidoyl and acid chloride, 2-benzothiazole, or 1-benzotriazole group
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We have newly synthesized the non-symmetrical "phthalimidoyl active ester" bi-dentate cross-linking reagents having an acid chloride, 2-benzothiazole, or 1-benzotriazole group (i.e., 9, 15, and 16) on the basis of the reactivity study of the "active ester" model compounds, 11-14, toward the various nucleophiles and examined their reaction selectivity towards the same nucleophiles. Then, we applied for the modification of cholesterol at the more reactive site of the bi-dentate linkers to give 3β-cholesteryl 4-(phthalimidoyloxycarbonyl)butyrate (39), and the subsequent reaction of 39 with several amines, such as benzylamine, 4-chlorobenzylamine, 2-phenylethylamine, l-phenylalanine methyl ester, or diphenylalanine benzyl ester as a protein model of the cholesterol antigen.
- Sheikh, Md. Chanmiya,Takagi, Shunsuke,Sakai, Mebumi,Mori, Tasuya,Hayashi, Naoto,Fujie, Tetsuo,Ono, Shin,Yoshimura, Toshiaki,Morita, Hiroyuki
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p. 1244 - 1254
(2011/04/15)
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- Nucleophilic iron catalysis in transesterifications: Scope and limitations
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Figure presented The ester bond is one of the most common structural motifs found in nature. Apart from the condensation between an acid and an alcohol, transesterifications represent another mechanistic alternative for the preparation of this compound class. The present paper summarizes our most recent investigations in this field, using nucleophilic iron complexes as catalysts for transesterifications under neutral conditions. This new type of metal catalyst complements the existing methodologies, which rely on Lewis acidic metal complexes. Investigations on scope and limitations, stereochemical course, and chemoselectivities will be presented.
- Magens, Silja,Plietker, Bernd
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supporting information; experimental part
p. 3715 - 3721
(2010/08/07)
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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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- Efficient condensation of carboxylic acids with alcohols catalyzed by fluorous ammonium triflates
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The use of fluorous ammonium salts as metal-free catalysts for the direct condensation of equimolar amounts of carboxylic acids and aliphatic alcohols has been investigated. Esterification reactions were thus conveniently carried out under mild fluorous biphasic conditions, in the presence of 1 mol % of fluorous ammonium triflate and without recourse to any additional water removal technique. Good to excellent ester yields were obtained in the case of primary and secondary aliphatic alcohols. The fluorous salt was easily recovered by simple phase separation and reused at least three times without considerable loss of activity.
- Mercs, László,Pozzi, Gianluca,Quici, Silvio
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p. 3053 - 3056
(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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- 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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- The Surface of Silica as a Medium for the Radical and Ionic Decomposition of Diacyl Peroxides
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The rates of decomposition of β-phenylpropionyl peroxide 1, β-phenylisovaleryl peroxide 2, and β-phenylisovaleryl p-nitrobenzoyl peroxide 3 are much higher on silica surfaces than they are in solution.The products formed on silica surfaces are derived from both radical and ionic precursors except in the case of 3, for which the reaction may be entirely ionic.The relationships between the medium effects on the rates and on the products suggest that the ionic and radical parts of the reaction branch from a common polar intermediate.Both the ionic and radical products differ significantly from those formed in solution.In the neophyl radical, adsorption inhibits the migration of phenyl to form phenyl-tert-butyl radical.In the ionic reaction, there is extensive migration of methyl in competition with phenyl, in contrast to the behavior of neophyl derivatives in solvolysis reaction.Dihydrocoumarin, from 1, and dimethyldihydrocoumarin, from 2 and 3, are not formed at all in solution.Esters, which are often formed via carboxy inversion and related reactions when polar diacyl peroxides decompose in solution, appear to arise from electron transfer in radial-pair precursors.There is no evidence of carboxy inversion compounds or carbonic acid esters in the physically adsorbed products, although some RO-C(=O)+ groups (1-2percent) appear to be trapped by the silica.Rearranged and unrearranged neophyl cations are trapped more extensively as silyl ethers.Other ion-derived products are one of the phenylisobutylenes, several phenylbutenes, and the carboxylic acids.Coadsorbed oxygen or acetonitrile alters the product distribution partly by trapping radicals and partly by site preemption effects.
- Leffler, J.E.,Barbas, J.T.
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p. 7768 - 7773
(2007/10/02)
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- Ketone-derived Peroxides. III. Decompositions of Cyclic Diperoxides derived from Dialkyl Ketones
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The decompositions of diperoxides from acetone, pentan-3-one, 1,5-diphenylpentan-3-one, pinacolone, benzyl methyl ketone and dibenzyl ketone have been studied.The yield of ketone decreases in this series, from 68percent with acetone to 1-2percent with dibenzyl ketone, i.e. with the increasing stability of the more stable radical fragment.The major products from the decompositions of diperoxides from the dibenzyl ketone and di(p-methylbenzyl) ketone were bibenzyl and 4,4'-dimethylbibenzyl respectively formed through coupling of benzyl radicals; crossover experiments showed that this was primarily an out-of-cage process.Most of the peroxides gave significant yields (5-20percent) of esters formed by an in-cage reaction between the alkyl radical and diacyl peroxide generated from decomposition of the biradical formed in the initial O-O bond homolysis of the peroxide.
- McCullough, Kevin J.,Morgan, Alistair R.,Nonhebel, Derek C.,Pauson, Peter L.
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p. 651 - 676
(2007/10/02)
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