- Ruthenium-catalysed domino hydroformylation-hydrogenation-esterification of olefins
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A novel catalytic domino reductive hydroformylation-esterification of olefins is reported. The optimal protocol makes use of an inexpensive Ru carbonyl catalyst and uses acetic acid as both solvent and reactant. In general, moderate to good yields are obtained using aliphatic or aromatic olefins including industrially relevant di-isobutene. This atom-efficient catalytic transformation provides straightforward access to various acetate esters from unfunctionalized olefins.
- Beller, Matthias,Dühren, Ricarda,Franke, Robert,Jackstell, Ralf,Kucmierczyk, Peter,Schneider, Carolin
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p. 5777 - 5780
(2021/09/10)
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- Tropolonate salts as acyl-transfer catalysts under thermal and photochemical conditions: Reaction scope and mechanistic insights
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Acyl-transfer catalysis is a frequently used tool to promote the formation of carboxylic acid derivatives, which are important synthetic precursors and target compounds in organic synthesis. However, there have been only a few structural motifs known to efficiently catalyze the acyl-transfer reaction. Herein, we introduce a different acyl-transfer catalytic paradigm based on the tropolone framework. We show that tropolonate salts, due to their strong nucleophilicity and photochemical activity, can promote the coupling reaction between alcohols and carboxylic acid anhydrides or chlorides to give products under thermal or blue light photochemical conditions. Kinetic studies and density functional theory calculations suggest interesting mechanistic insights for reactions promoted by this acyl-transfer catalytic system.
- Mai, Binh Khanh,Koenigs, Rene M.,Nguyen, Thanh Vinh,Lyons, Demelza J.M.,Empel, Claire,Pace, Domenic P.,Dinh, An H.
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p. 12596 - 12606
(2020/11/18)
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- Iron-Catalysed Remote C(sp3)?H Azidation of O-Acyl Oximes and N-Acyloxy Imidates Enabled by 1,5-Hydrogen Atom Transfer of Iminyl and Imidate Radicals: Synthesis of γ-Azido Ketones and β-Azido Alcohols
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In the presence of a catalytic amount of iron(III) acetylacetonate [Fe(acac)3], the reaction of structurally diverse ketoxime esters with trimethylsilyl azide (TMSN3) afforded γ-azido ketones in good to excellent yields. This unprecedented distal γ-C(sp3)?H bond azidation reaction went through a sequence of reductive generation of an iminyl radical, 1,5-hydrogen atom transfer (1,5-HAT) and iron-mediated redox azido transfer to the translocated carbon radical. TMSN3 served not only as a nitrogen source to functionalise the unactivated C(sp3)?H bond, but also as a reductant to generate the catalytically active FeII species in situ. Based on the same principle, a novel β-C(sp3)?H functionalisation of alcohols via N-acyloxy imidates was subsequently realised, leading, after hydrolysis of the resulting ester, to β-azido alcohols, which are important building blocks in organic and medicinal chemistry.
- Torres-Ochoa, Rubén O.,Leclair, Alexandre,Wang, Qian,Zhu, Jieping
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p. 9477 - 9484
(2019/05/21)
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- Esterification of Tertiary Amides by Alcohols Through C?N Bond Cleavage over CeO2
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CeO2 has been found to promote ester forming alcoholysis reactions of tertiary amides. The present catalytic system is operationally simple, recyclable, and it does not require additives. The esterification process displays a wide substrate scope (>45 examples; up to 93 % isolated yield). Results of a density functional theory (DFT) study combined with in situ FT-IR observations indicate that the process proceeds through rate limiting addition of a CeO2 lattice oxygen to the carbonyl group of the adsorbed acetamide species with energy barrier of 17.0 kcal/mol. This value matches well with experimental value (17.9 kcal/mol) obtained from analysis of the Arrhenius plot. Further studies by in situ FT-IR and temperature programmed desorption using probe molecules demonstrate that both acidic and basic properties are important, and consequently, CeO2 showed the best performance for the C?N bond cleavage reaction.
- Toyao, Takashi,Nurnobi Rashed, Md.,Morita, Yoshitsugu,Kamachi, Takashi,Hakim Siddiki,Ali, Md. A.,Touchy,Kon, Kenichi,Maeno, Zen,Yoshizawa, Kazunari,Shimizu, Ken-ichi
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p. 449 - 456
(2018/09/11)
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- Lipase-mediated selective acetylation of primary alcohols in ethyl acetate
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An environmental friendly process to selectively acetylate primary alcohols was demonstrated. The esterification process consists of treatment of a primary alcohol in the presence of immobilized C. antarctica lipase (Novozyme-435) in ethyl acetate at room temperature. Primary alcohols were acetylated in the presence of secondary alcohols and phenols.
- de Souza, Ernane C.,Romero-Ortega, Moises,Olivo, Horacio F.
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supporting information
p. 287 - 290
(2017/12/29)
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- Light-enhanced acid catalysis over a metal-organic framework
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A Br?nsted acid-functionalized metal-organic framework (MOF), MIL-101-SO3H, was prepared for acid-engaged esterification reactions. Strikingly, for the first time, the MOF exhibits significantly light-enhanced activity and possesses excellent activity and recyclability, with even higher activity than H2SO4 under light irradiation.
- Xu, Caiyun,Sun, Keju,Zhou, Yu-Xiao,Ma, Xiao,Jiang, Hai-Long
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supporting information
p. 2498 - 2501
(2018/03/21)
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- Supported palladium nanoparticles as switchable catalyst for aldehyde conjugate/s and acetate ester syntheses from alcohols
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Polymer-supported Pd(0) (Pd@PS) nanoparticles (NPs) were explored as a switchable catalyst for oxidative aldehyde conjugate/s (AC/s) and acetate esters (AEs) syntheses from alcohols. Using the same substrates, the catalyst in the presence of oxygen and K2CO3 participated in AC/s synthesis, and in the presence of traces of air and NaOtBu, unusual AEs products were obtained.
- Kumar, Sandeep,Chaudhary, Abha,Bandna,Bhattacherjee, Dhananjay,Thakur, Vandna,Das, Pralay
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supporting information
p. 3242 - 3245
(2017/07/12)
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- Novel access to carbonyl and acetylated compounds: The role of the tetra-: N -butylammonium bromide/sodium nitrite catalyst
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A novel aerobic oxidation of alcohols without the use of any oxidants was developed. An equimolar catalytic mixture of tetra-n-butylammonium bromide and sodium nitrite catalyzes the aerobic selective oxidation of benzylic alcohols under oxidant-free, base-free and metal-free conditions. The mild reaction conditions allow oxidation of a wide range of benzylic alcohols, chemo-selectively to their carbonyl compounds (68-93% isolated yields). More importantly, high selectivity among different kinds of alcohols (aromatic vs. aliphatic alcohols, primary vs. secondary alcohols as well as alcohols having neutral rings vs. electron-deficient rings) is available by this approach. The method surprisingly switched over to be an efficient acetylation approach in the case of aliphatic alcohols without the use of any transition metal, phosphorous or other toxic reagents or any need for using toxic acyl halides, sulfonyl halides, anhydrides, etc. by the use of only acetic acid as a reagent.
- Sheykhan, Mehdi,Moafi, Hadi Fallah,Abbasnia, Masoumeh
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p. 51347 - 51355
(2016/06/09)
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- Oxidative "reverse-esterification" of ethanol with benzyl/alkyl alcohols or aldehydes catalyzed by supported rhodium nanoparticles
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A very unusual role of polystyrene stabilized rhodium (Rh@PS) nanoparticles as a supported catalyst is described for "reverse-esterification" of ethanol with benzyl/alkyl alcohols or aldehydes. Faster and selective oxidation of ethanol to acetaldehyde and H2 under Rh@PS catalyzed conditions which restricted further oxidation of benzyl/alkyl alcohols and their in situ reaction gave the corresponding acetate esters following the dehydrogenative-coupling approach. A hitherto redox dehydrogenative-coupling of ethanol and aldehydes has also been explored for the same acetate ester synthesis under Rh@PS catalyzed conditions.
- Guha, Nitul Ranjan,Sharma, Saurabh,Bhattacherjee, Dhananjay,Thakur, Vandna,Bharti, Richa,Reddy, C. Bal,Das, Pralay
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supporting information
p. 1206 - 1211
(2016/03/09)
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- Transition metal nanoparticles stabilized by ammonium salts of hyperbranched polystyrene: effect of metals on catalysis of the biphasic hydrogenation of alkenes and arenes
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Abstract Hyperbranched polystyrene bearing ammonium salts (HPS-NR3+Cl-) behaves as an excellent stabilizer of ruthenium, rhodium, iridium, palladium, and platinum nanoparticles from 1 to 3 nm in size uniformly dispersed in the polymer matrix. The catalytic performance of the resulting metal-polymer composites, M@HPS-NR3+Cl-, is dependent on the metal. This dependence was investigated by assessing the hydrogenation of alkenes and arenes. The utility of M@HPS-NR3+Cl- as reusable catalysts in aqueous/organic biphasic systems was demonstrated by examining the catalysis of the hydrogenation of aromatic compounds containing various functional groups by Ru@HPS-NR3+Cl-.
- Gao, Lei,Kojima, Keisuke,Nagashima, Hideo
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p. 6414 - 6423
(2015/08/18)
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- Chemoselective palladium-catalyzed oxidation of vinyl ether to acetate using hydrogen peroxide
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A practical and environmental-friendly method was developed to convert vinyl ether into acetate by using a palladium complex with phosphine ligand and hydrogen peroxide. The only by-product is water. Chemoselective oxidation of vinyl ether and tert-enamides to form acetate and N-acetyl amide with hydrogen peroxide in the presence of palladium complex having phosphine ligand was developed under mild reaction conditions. This process is environmentally friendly because it uses hydrogen peroxide as a clean oxidant, with water being the only byprocuct.
- Kon, Yoshihiro,Tanaka, Shinji,Nakashima, Takuya,Sato, Kazuhiko,Shimada, Hiromichi
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p. 749 - 756
(2014/07/22)
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- Palladium-catalyzed oxidation of vinyl ether to acetate with hydrogen peroxide
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The selective hydrogen peroxide oxidation of vinyl ethers to give acetates was developed using triphenylphosphine palladium and triethyl amine catalysts under mild reaction conditions.
- Kon, Yoshihiro,Chishiro, Takefumi,Imao, Daisuke,Nakashima, Takuya,Nagamine, Takashi,Hachiya, Houjin,Sato, Kazuhiko
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supporting information; experimental part
p. 6739 - 6742
(2011/12/22)
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- Rhodium/graphite-catalyzed hydrogenation of carbocyclic and heterocyclic aromatic compounds
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Rhodium on graphite (Rh/Gr, C24Rh) was prepared by reaction of anhydrous rhodium trichloride with potassium graphite (C8K, 3 equivalents) and used as a heterogeneous catalyst for the hydrogenation of carbocyclic and heterocyclic aromatic compounds at room temperature and 1 atm of hydrogen pressure. The effect of substitution on the benzene ring was examined in a variety of derivatives, including those with alkyl, hydroxy, alkoxy, aryloxy, carboxy, amino, nitro, acyl, chloro, or functionalized alkyl groups. Reduction of carbonyl functions of aromatic aldehydes and ketones occurred with complete or partial cleavage of the benzylic C-O bond; this cleavage also occurred in the hydrogenation of benzylic alcohols and esters. Georg Thieme Verlag Stuttgart.
- Falini, Giuseppe,Gualandi, Andrea,Savoia, Diego
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experimental part
p. 2440 - 2446
(2010/02/27)
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- An amino alcohol ligand for highly enantioselective addition of organozinc reagents to aldehydes: Serendipity rules
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(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.
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p. 2133 - 2136
(2007/10/03)
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- Cleavage of 2-methoxyethoxymethyl ethers catalyzed by cerium(IV) ammonium nitrate (CAN) in acetic anhydride
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The reactions of 2-methoxyethoxymethyl (MEM) ethers 1 with a catalytic amount of cerium(IV) ammonium nitrate (CAN) in acetic anhydride gave the corresponding mixed acetal esters 2 and acetates 3.
- Tanemura, Kiyoshi,Suzuki, Tsuneo,Nishida, Yoko,Satsumabayashi, Koko,Horaguchi, Takaaki
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p. 1012 - 1013
(2007/10/03)
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- Acetylation and formylation of alcohols with triphenylphosphine and carbon tetrabromide in ethyl acetate or ethyl formate
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Alcohols were acetylated or formylated with triphenylphosphine and carbon tetrabromide in ethyl acetate or ethyl (or methyl) formate at room temperature. THP or TBDMS ether of primary alcohol got converted into formate or acetate under the experimental conditions employed in one pot operation.
- Hagiwara, Hisahiro,Morohashi, Kimie,Sakai, Hitoshi,Suzuki, Toshio,Ando, Masayoshi
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p. 5845 - 5852
(2007/10/03)
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- Acylation of alcohols and amines with vinyl acetates catalyzed by Cp*2Sm(thf)2
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Cp*2Sm(thf)2 was found to be an efficient catalyst for the acylation of alcohols and amines with esters under mild conditions. In the present acylation, vinyl and isopropenyl acetates served as good acylating agents. Thus, a variety of alcohols and amines underwent acylation with vinyl and isopropenyl acetates in the presence of Cp*2Sm(thf)2 to give the corresponding esters and amides in good to excellent yields. This catalytic acylation of alcohols and amines offers an additional useful method by the use of various esters, instead of acid anhydrides and acid chlorides, as acylating agents under very mild conditions.
- Ishii, Yasutaka,Takeno, Mitsuhiro,Kawasaki, Yumi,Muromachi, Akifumi,Nishiyama, Yutaka,Sakaguchi, Satoshi
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p. 3088 - 3092
(2007/10/03)
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- Effects of Substrate Structure on Lipase-Catalyzed Transesterification of ω-Substituted 1-Alkanols in Organic Solvents.
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Lipase-catalyzed transesterification of ω-phenyl-1-alkanols with vinyl acetate in organic solvents have been investigated.Benzyl alcohol is the most reactive substrate among those studied.It is proposed that a lipase from Pseudomonas cepacia (PCL) has a domain to attract an aromatic moiety of a substrate.
- Nakamura, Kaoru,Kawasaki, Masashi,Ohno, Atsuyoshi
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p. 3053 - 3056
(2007/10/02)
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- Cobalt(II) Chloride Catalyzed Acylation of Alcohols with Acetic Anhydride: Scope and Mechanism
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Cobalt(II) chloride catalyzes the acetylation of a variety of alcohols with acetic anhydride in excellent yield.Primary hydroxyl groups can be selectively acylated in the presence of secondary and tertiary ones while the secondary hydroxyl groups can be preferentially acetylated in the presence of tertiary ones.Tertiary alcohols have been found to give ketones, acetoacetates, olefins, and diketene in addition to the acetate.The β-hydroxy esters and ketones can be acylated under these conditions without any elimination, and this reaction has been compared with 4-(dimethylamino)pyridine (DMAP)-mediated acylations where elimination of the resulting β-acetoxy carbonyl compound is observed.A detailed investigation of the acylation of tertiary alcohols has revealed that these reactions proceed via a tertiary alkoxy radical and ketene.A mechanism for these acylations is proposed by invoking an electron-transfer process.
- Iqbal, Javed,Srivastava, Rajiv Ranjan
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p. 2001 - 2007
(2007/10/02)
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- A LEWIS ACID-CATALYZED PROCEDURE FOR THE CONVERSION OF 2-METHOXYETHOXYMETHYL ETHERS TO CARBOXYLIC ESTERS
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A procedure for the conversion of 2-methoxyethoxymethyl (MEM) ethers to carboxylic esters employed ferric chloride (0.4 equivalents) and a carboxulic anhydride (14 equivalents) and exibited selectivity for the MEM ether functionality in the presence of benzyl ethers.
- Gross, Raymond S.,Watt, David S.
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p. 1749 - 1760
(2007/10/02)
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- Mercury-assisted solvolyses of alkyl halides. Simple procedures for the preparation of nitrate esters, acetate esters, alcohols and ethers
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The reactions of a wide variety of alkyl halides with mercury(I) and/or (II) nitrate in 1,2-dimethoxyethane, mercury(II) acetate in acetic acid, aqueous mercury(II) perchlorate, and mercury(II) perchlorate in alcohol solvents have been investigated; as a result, simple high yield procedures for the conversion of alkyl halides into the corresponding nitrate esters, acetate esters, alcohols and ethers have been developed.
- McKillop,Ford
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p. 2467 - 2475
(2007/10/05)
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