- Methanesulfonic anhydride-promoted sustainable synthesis of thioesters from feedstock acids and thiols
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Abstract: An unprecedented metal-, halogen- and solvent-free, MSAA-promoted S-carbonylation of thiols with feedstock acids has been developed. This new transformation provides an efficient and atom-economic strategy for the synthesis of thioesters in a single operation from readily available and inexpensive starting materials. The reaction avoids the use of expensive and hazardous coupling reagents, bases and generates water as the only by-product, thus making this chemical synthetic process more viable, environment-friendly and contributing towards sustainable chemistry. Graphic abstract: [Figure not available: see fulltext.].
- Singh, Pallavi,Peddinti, Rama Krishna
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- Green synthesis and antibacterial activity of chalcogenoesters
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Abstract: Herein, we present a new variation for an eco-friendly methodology for the synthesis of chalcogenoester in good-to-excellent yields in a short time, with an easy work-up/purification step, and in a greenest methodology, affording the minimum gen
- Baldisserotto, Bernardo,Dornelles, Luciano,Junior, Guerino B.,Ravanello, Bruno B.,Rodrigues, Oscar E. D.,Santos, Roberto C. V.,Soares, Letiére C.,da Rosa, Fernanda H.,da Silva, Rafael S.,de A. Vaucher, Rodrigo,dos S. Barboza, Victor
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- A synthesis of biaryl ketones via the C–S bond cleavage of thiol ester by a Cu/Ag salt
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We report the synthesis of biaryl ketones via an unprecedented copper/silver catalyzed acylative cross-coupling of thiol esters with either an arylboronic acid or a potassium aryltrifluoroborate. This new method proceeds without a requisite Pd-catalyst and Cu(I)TC mediator, and is efficient, versatile, operationally simple, and accommodating functionally diverse thiol esters, arylboronic acids, and potassium aryltrifluoroborates.
- Ghosh, Prasanjit,Ganguly, Bhaskar,Das, Sajal,Perl, Eliyahu
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supporting information
p. 2751 - 2756
(2017/06/23)
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- Harnessing the catalytic behaviour of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP): An expeditious synthesis of thioesters
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A novel, efficient, metal-, base- and acid-free straightforward protocol has been developed for the construction of useful thioesters. The immense catalytic potential of HFIP for promoting the thiocarbonylation of acyl halides and thiols is disclosed. HFIP was recovered with ease and reused for further reactions without any loss of reactivity. Both aryl and alkyl thiols bearing electron-donating and electron-withdrawing groups as well as aryl- and alkyl acyl halides worked well in this reaction. Inexpensive precursors, short reaction time, obviating workup, high atom economy, and gram-scale preparation are the significant features of the developed eco-friendly route for S-carbonylation of thiols.
- Singh, Pallavi,Peddinti, Rama Krishna
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supporting information
p. 1875 - 1878
(2017/04/21)
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- Polymer supported Pd catalyzed thioester synthesis via carbonylation of aryl halides under phosphine free conditions
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A new polymer supported phosphine free Pd(ii) complex has been synthesized and characterized. The catalytic performance of the complex has been tested for the carbonylation of aryl halides into aryl thioesters under mild reaction conditions. Thioesters were obtained in excellent yields from various aryl iodides and thiols in the presence of carbon monoxide and polymer supported palladium catalyst. The effects of solvent, base, reaction time and catalyst amount for the thioester synthesis were reported. This catalyst showed excellent catalytic activity and recyclability. The polymer supported Pd(ii) catalyst could be easily recovered by filtration and reused more than five times without appreciable loss of its initial activity.
- Islam, Sk Manirul,Molla, Rostam Ali,Roy, Anupam Singha,Ghosh, Kajari
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p. 26181 - 26192
(2014/07/08)
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- Pd-catalyzed thiocarbonylation with stoichiometric carbon monoxide: Scope and applications
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A general protocol for the Pd-catalyzed thiocarbonylation of aryl iodides with stoichiometric carbon monoxide has been established employing a catalytic system composed of Pd(OAc)2 and DPEphos with low catalyst loading (1 mol %). Both electron-rich and -deficient aryl iodides proved effective for these couplings with aryl and alkyl thiols. The choice of the metal ligands and the solvent system was crucial for the efficiency and chemoselectivity of these transformations.
- Burhardt, Mia N.,Taaning, Rolf H.,Skrydstrup, Troels
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supporting information
p. 948 - 951
(2013/03/28)
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- Synthesis of thiol esters using nano CuO/Ionic liquid as an eco-friendly reductive system under microwave irradiation
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We report an efficient, fast, and environmentally friendly method for the synthesis of a wide range of thiol esters using stable diorganoyl disulfides and acyl chlorides, using CuO nanoparticles and [pmim]Br as the reductive system. This method gave good to excellent isolated yields of the desired products after only three minutes of microwave irradiation. Furthermore, by using the same green approach, we were also able to synthesize thiocarbonates bearing interesting functionalities. We report an efficient, fast, and environmentally friendly method for the synthesis of thiol esters starting from diorganoyl disulfides and acyl chlorides, and using CuO nanoparticles and [pmim]Br as the reductive system. This approach gave good to excellent isolated yields of the desired products in only three minutes under microwave irradiation. Copyright
- Azeredo, Juliano B.,Godoi, Marcelo,Schwab, Ricardo S.,Botteselle, Giancarlo V.,Braga, Antonio L.
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supporting information
p. 5188 - 5194
(2013/11/06)
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- The direct thioesterification of aldehydes with disulfides via NHC-catalyzed carbonyl umpolung strategy
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An efficient N-heterocyclic carbene (NHC)-catalyzed direct thioesterification of aldehydes and α,β-unsaturated aldehydes (enals) with diaryl disulfides is reported. The protocol involves carbonyl umpolung reactivity of aldehydes and enals in which the car
- Singh, Santosh,Yadav, Lal Dhar S.
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experimental part
p. 5136 - 5140
(2012/09/22)
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- Zn in ionic liquid: An efficient reaction media for the synthesis of diorganyl chalcogenides and chalcogenoesters
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A straightforward and efficient methodology is described to synthesize structurally diverse diorganyl selenides, sulfides, seleno- and thioesters by using commercially available Zn dust in ionic liquid. Excellent yields were achieved under neutral conditions at room temperature in a short time. The solvent/ionic liquid is reusable and exhibited higher performance as compared with organic solvents.
- Narayanaperumal, Senthil,Alberto, Eduardo E.,Gul, Kashif,Kawasoko, Cristiane Yuriko,Dornelles, Luciano,Rodrigues, Oscar E.D.,Braga, Antonio Luiz
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experimental part
p. 4723 - 4730
(2011/06/27)
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- A new odorless one-pot synthesis of thioesters and selenoesters promoted by Rongalite
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Rongalite promotes cleavage of diaryl disulfides generating chalcogenolate anions that then undergo facile acylation with anhydrides in the presence of CsF to afford thioesters (3) with good to excellent yields. By using the present protocol, 5-arylthio-5-oxopentanoic acid (4) can be facilely prepared. The important features of the methodology are broad substrate scope, simple operation, and no requirement for metal catalysts. It is noteworthy that acylations of diphenyl diselane with anhydrides are also conducted smoothly to afford selenoesters (5) in good yields under the standard conditions.
- Dan, Weixing,Deng, Hongjuan,Chen, Jiuxi,Liu, Miaochang,Ding, Jinchang,Wu, Huayue
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experimental part
p. 7384 - 7388
(2010/10/02)
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- Convenient and efficient synthesis of thiol esters using zinc oxide as a heterogeneous and eco-friendly catalyst
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A catalytic method was developed to synthesize thiol esters from the reaction of acyl chlorides and thiols using zinc oxide as a catalyst under solvent-free conditions at room temperature. Mild reaction conditions, short reaction time, excellent yields of products and recyclability of the catalyst are noteworthy features of this methodology. CSIRO 2008.
- Bandgar, Babasaheb Pandurang,More, Parmeshwar Eknath,Kamble, Vinod Tribhuvannathji,Sawant, Sanjay Suresh
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experimental part
p. 1006 - 1010
(2009/04/05)
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- Kinetics of the reaction of substituted 4-nitrophenyl benzoates with benzenethiol in the presence of potassium carbonate in dimethylformamide
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The effect of the substituent nature on the rate and activation parameters of transesterification of a series of 4-nitrophenyl benzoates with benzenethiol in dimethylformamide in the presence of potassium carbonate was studied by the competing reaction method. In all cases, change of the Gibbs energy of activation is determined mainly by variation of the enthalpy of activation. 4-Nitrophenyl benzoates having electron-withdrawing substituents in the benzoyl fragment were found to fit an isokinetic relation with an isokinetic temperature β of 318 K. Enthalpy-entropy compensation effect was observed in the reactions with all the examined 4-nitrophenyl benzoates. The relation between the reactivity and polarizability of nucleophilic center in S-and O-nucleophiles is discussed.
- Os'kina,Vlasov
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experimental part
p. 561 - 569
(2009/04/05)
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- Effective esterification of carboxylic acids using (6-oxo-6H-pyridazin-1-yl)phosphoric acid diethyl ester as novel coupling agents
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(6-Oxo-6H-pyridazin-1-yl)phosphoric acid diethyl esters (3) are efficient and selective coupling agents for equimolar esterification of carboxylic acids and alcohols. Esterification of aliphatic and aromatic carboxylic acids with aliphatic and aromatic alcohols using 3 afforded the corresponding esters chemoselectively in good to excellent yield.
- Won, Ju-Eun,Kim, Ho-Kyun,Kim, Jeum-Jong,Yim, Heong-Seup,Kim, Min-Jung,Kang, Seung-Beom,Chung, Hyun-A.,Lee, Sang-Gyeong,Yoon, Yong-Jin
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p. 12720 - 12730
(2008/03/14)
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- Dess-Martin periodinane mediated synthesis of thioesters from aldehydes
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Dess-Martin periodinane (DMP) mediated efficient synthesis of thioesters from the corresponding aldehydes under mild conditions is described.
- Bandgar, Sunita B.,Bandgar,Korbad,Sawant
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p. 1287 - 1290
(2007/10/03)
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- Kinetics and Mechanism of the Aminolysis of S-Phenyl Thiobenzoates
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Kinetic studies on the nucleophilic substitution reaction of S-phenyl thiobenzoates with anilines have been carried out at 55.0 deg C.Effects of substituents in the nucleophile(X), substrate(Y) and leaving groups(Z) are analyzed in terms of Hammett's and Broensted's coefficients, ρi and βi and cross-interaction constants ρij and βij where i and j denote X, Y or Z.The sign of ρXZ (or βXZ) is positive, and accordingly, the transition state(TS) variations with the substituents are consistent with those predicted by the potential energy surface diagram; the magnitude of ρx(βx) and ρxy decreases with a better leaving group, and that of ρz and βz decreases with a stronger nucleophile leading to an earlier TS, in agreement with a normal Hammond effect.The larger magnitudes of ρXY, ρYZ and βXZ suggest that the reaction proceeds by an associative SN2 mechanism.A greater kH/kD value (1.0) is observed with deuterated aniline nucleophiles for a stronger nucleophile and a better leaving group, supporting the earlier TS proposed on the basis of the cross-interaction constants.The inverse secondary kinetic isotope effects obtained preclude involvement of any four-center TS or base catalysis by aniline.
- Lee, Ikchoon,Shim, Chang Sub,Lee, Hai Whang
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p. 769 - 793
(2007/10/02)
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- REACTIONS OF ORGANOMETALLIC COMPOUNDS CATALYZED BY TRANSITION-METAL COMPLEXES. XV. PRODUCTION OF THIOCARBOXYLIC S-ESTERS BY CATALYTIC CARBONYLATION OF ARYL IODIDES AND TRIETHYLTIN THIOLATES
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Carbonylation in the aryl iodide-triethyltin thiolate system, catalyzed by bis(triphenylphosphine) palladium, was studied.In the case of unactivated aryl iodides containing weak electron-withdrawing substituents thiocarboxylic S-esters are formed with satisfactory yields.The reactions of aryl iodides containing strong electron-withdrawing groups lead mainly to the products from cross-coupling, i.e., unsymmetrical sulfides.The mechanism of the catalytic action of the phosphine complex of palladium was investigated.
- Gulevich, Yu. V.,Bumagin, N. A.,Beletskaya, I. P.
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p. 1918 - 1923
(2007/10/02)
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- Facile Conversions of Carboxylic Acids into Amides, Esters, and Thioesters Using 1,1'-Oxalyldiimidazole and 1,1'-Oxalyldi(1,2,4-triazole)
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Aliphatic, aromatic, and heteroaromatic carboxylic acids react with 1,1'-oxalyldiimidazole (1) or 1,1'-oxalyldi(1,2,4-triazole) (2) in acetonitrile for 40 min at 40 degC to give the corresponding 1-acylazole intermediates (11), which promptly undergo aminolysis and alcoholysis to form amides (13) including dipeptides (14), esters (16), and thioesters (19).These findings show that both 1 and 2 can be utilized as condensing reagents for the synthesis of carboxylic acid derivatives.Keywords --- 1,1'-oxalyldiimidazole; 1,1'-oxalyldi(1,2,4-triazole); 1,1'-carbonyldiimidazole; 1-acylazole; condensing reagent; amidation; esterification; dipeptide; aminolysis; alcoholysis
- Kitagawa, Tokujiro,Kuroda, Hiroko,Sasaki, Hideaki,Kawasaki, Koichi
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p. 4294 - 4301
(2007/10/02)
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- PALLADIUM-CATALYZED SYNTHESIS OF AROMATIC ACID DERIVATIVES BY CARBONYLATION OF ARYL IODIDES AND Alk3SnNu (Nu = MeO, Et2N, PhS, EtS)
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Carbonylation of the ArI/Alk3SnNu system (Nu = MeO, Et2N), leading to esters and amides of substituted benzoic acids, occurs readily in the presence of phosphinepalladium complexes.When Nu = PhS and EtS either a cross-coupling product (Ar = p-NO2C6H4) or a carbonylation product (Ar = Ph) is formed predominantly, depending on the nature of ArI.Stoichiometric reactions of ArPdI(PPh3)2 with carbon monoxide, resulting in acylpalladium complexes, and reactions of ArCOPdI(PPh3)2 with Alk3SnNu have been studied.Some mechanistic aspects are discussed.
- Bumagin, N. A.,Gulevich, Yu. V.,Beletskaya, I. P.
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p. 415 - 418
(2007/10/02)
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