- Nickel-catalyzed carbonylation of thioacetates with aryl iodides via CO insertion and C–S bond cleavage
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Aryl thioesters are synthesized via nickel-catalyzed carbonylation of thioacetates with aryl iodides. Alkyl thioacetates undergo coupling with carbon monoxide and aryl iodides to produce the desired aryl thioesters in moderate yields. This catalytic carbonylative coupling process provides a cost-effective and direct approach for the preparation of useful thioesters.
- Lu, Kui,Lv, Ming-Xiu,Mai, Wen-Peng,Sui, Hong-Da
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p. 890 - 895
(2021/07/02)
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- Nickel-Catalyzed Thiocarbonylation of Arylboronic Acids with Sulfonyl Chlorides for the Synthesis of Thioesters
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An interesting procedure for thioester synthesis via nickel-catalyzed thiocarbonylation of arylboronic acid with sulfonyl chlorides as the sulfur source has been explored. Using Mo(CO)6 as a solid CO surrogate and reductant, a broad range of thioesters were obtained in moderate to good yields with good functional group tolerance.
- Qi, Xinxin,Bao, Zhi-Peng,Yao, Xin-Tong,Wu, Xiao-Feng
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supporting information
p. 6671 - 6676
(2020/09/02)
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- Regio- and Stereoselective Chan-Lam-Evans Enol Esterification of Carboxylic Acids with Alkenylboroxines
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Efficient and scalable Cu(II)-mediated enol esterification methodology of carboxylic acids from alkenyl boroxines and boronic acids is presented. The reaction shows a wide scope in aliphatic and aromatic carboxylic acids in combination with several alkenyl boroxines. In the case of 2-substituted alkenyl boroxines the double bond configuration was fully retained in the enol ester product. Also N-hydroxyimides and imides could be transformed in the respective amidooxy vinyl enol ethers and vinyl enamides. Finally, with the exception of methionine, all other 19 canonical amino acids showed their compatibility to give the enol esters in a stereoselective fashion. (Figure presented.).
- Steemers, Luuk,Wijsman, Linda,van Maarseveen, Jan H.
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supporting information
p. 4241 - 4245
(2018/10/02)
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- Microwave-assisted direct thioesterification of carboxylic acids
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A one-pot synthesis of thioesters directly from carboxylic acids, N,N′-diphenylthiourea, triethylamine, and primary alkyl halides is described. Microwave-assisted heating and a catalytic amount of 4- (dimethylamino)pyridine (DMAP) further improved the yields. Both aromatic and aliphatic carboxylic acids were converted to the corresponding thioesters, and many functional groups were compatible with this reaction. Several possible reaction intermediates were investigated, and the quaternary ammonium salts, derived from alkyl halides and tertiary amines, were the intermediates to yield thioesters. A new reaction mechanism for this thioesterification is proposed.
- Chou, Yen-Lin,Jhong, Yi,Swain, Sharada Prasanna,Hou, Duen-Ren
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p. 10201 - 10208
(2018/05/31)
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- Investigations of the Thermal Responsiveness of 1,4,2-Oxathiazoles
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The first systematic study of the thermal rearrangement/fragmentation of 5,5-disubstituted 1,4,2-oxathiazoles into isothiocyanates is reported. Structure-activity relationships reveal that the choice of substituent at the 5-position of the 1,4,2-oxathiazoles is the predominant factor to influence the ease of fragmentation.
- Hewitt, Russell J.,Ong, Michelle Jui Hsien,Lim, Yi Wee,Burkett, Brendan A.
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supporting information
p. 6687 - 6700
(2015/10/29)
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- Syntheses of thiol and selenol esters by oxidative coupling reaction of aldehydes with RYYR (Y = S, Se) under metal-free conditions
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Thiol and selenol esters were synthesized by a direct oxidative coupling reaction of aldehydes with disulfides or diselenides in ethyl acetate under metal-free conditions. Among the oxidants examined, tert-butyl peroxide (TBP) was shown to give the best results. For the substrates with both electron-donating and electron-withdrawing substituents, the reaction proceeded smoothly and gave moderate to good yields. Compared with the previous method, the present route is very simple, atom-economical and environmentally friendly. This journal is the Partner Organisations 2014.
- He, Chunhuan,Qian, Xuewei,Sun, Peipei
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supporting information
p. 6072 - 6075
(2014/08/05)
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- Metathetic sulfur transfer mediated by N-(2-aminophenyl)-4-methyl- thiazolin-2-thione derivatives. Part III: An alkylthiol- and thioacid-free route to diversely substituted S-alkyl thioesters
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A metal free synthesis of S-alkyl thioesters, which does not involve alkylthiol or thiocarboxylic acid as sulfur source is disclosed. The process involves first an acylation at the nitrogen of the readily available N-(2-aminophenyl)-4-methyl-thiazolin-2-thione, second an alkylation at sulfur of the resulting amides and finally a base catalyzed metathetic reaction, which provides under very mild conditions and in high isolated yields the S-alkyl thioesters. An ion-pair intermediate (9-acyl-3-methyl[1,3]thiazolo[3,2-a][3,1] benzimidazol-9-ium alkylthiolate) accounts for the formation of mixed thioesters during cross-coupling experiments. S-Alkyl diversity is provided by the alkylating agent and the acyl diversity comes from the acylating agent, while the sulfur atom is provided by the heterocycle.
- Mehdid, Mohammed Amine,Djafri, Ayada,Andreoli, Federico,Vanthuyne, Nicolas,Farran, Daniel,Niebler, Johannes,Buettner, Andrea,Giorgi, Michel,Roussel, Christian
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p. 4994 - 5001
(2013/07/19)
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- Highly efficient iron(II) chloride/N-bromosuccinimide-mediated synthesis of imides and acylsulfonamides
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We have developed a general and highly efficient iron(II) chloride/N-bromosuccinimide (NBS)-mediated method for the synthesis of imides and acylsulfonamides via couplings of thioesters with carboxamides/sulfonamides, and the method is simple, economical and shows practical advantages.
- Wang, Feng,Liu, Hongxia,Fu, Hua,Jiang, Yuyang,Zhao, Yufen
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supporting information; experimental part
p. 246 - 252
(2009/09/05)
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- Synthesis of thioesters by simultaneous activation of carboxylic acids and alcohols using PPh3/NBS with benzyltriethylammonium tetrathiomolybdate as the sulfur transfer reagent
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A new and simple route for the synthesis of thioesters starting from carboxylic acids and alcohols is reported by using tetrathiomolybdate as the key sulfur transfer reagent, Triphenylphosphane and N-bromosuccinimide were used for the activation of the ca
- Gopinath, Purushothaman,Vidyarini, Ravindran Sasitha,Chandrasekaran, Srinivasan
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experimental part
p. 6043 - 6047
(2010/03/25)
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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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- Zinc promoted convenient and general synthesis of thiol esters
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Synthesis of thiol esters from acyl chlorides and thiols in the presence of activated zinc is described. The recovery of zinc and its reuse makes the procedure more economic.
- Meshram,Reddy, Gondi Sudershan,Bindu, K. Hima,Yadav
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p. 877 - 878
(2007/10/03)
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- Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 13.1 Extrusion of Ph3P from sulfinyl ylides and reactivity of the resulting sulfinyl carbenes
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Six α-sulfinyl phosphorus ylides 6 have been prepared and are found upon flash vacuum pyrolysis at 500°C to undergo mainly extrusion of Ph3P to give thioesters, presumably by 1,2-oxygen transfer in the initially formed sulfinyl carbenes; for α-arylsulfinyl ylides loss of Ph3PO to give additional products is also observed.
- Aitken, R. Alan,Drysdale, Martin J.,Ryan, Bruce M.
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p. 3345 - 3348
(2007/10/03)
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- Photochemical Reactions of Mercapto/Amino Substituted Alkyl Phenylglyoxylates Induced by Intramolecular Electron Transfer
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2'-Alyothio ethyl phenylglyoxylates (1) and 2'-dimethylamino ethyl phenylglyoxylate (10) were synthesized and their photochemistry studied.In contrast to their oxygen analog 3, which give normal Norrish type II cleavage products, the title compounds undergo intermolecular electron transfer from the heteroatom (sulfur/nitrogen) to the excited carbonyl group, followed by proton transfer and subsequent closing of the resulting biradical to produce seven-mebered (11) lactones in high yield.Thiadialkyl phenylglyoxylates (9) react inefficiently due to intramolecular self-quenching of phenylgluoxylate chromophores.The photoreactivity of α-oxothioester (14) was compared with that of its nitrogen (α-oxoamide) and oxygen (phenylglyoxylate) counterparts. - Keywords: Photochemical; Mercapto; Amino; Phenylglyoxylates; Electron Transfer
- Hu, Shengkui,Neckers, Douglas C.
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p. 2751 - 2766
(2007/10/03)
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- The Hydrolysis of Phthalide, Thiophthalide, and Methyl o-Methoxybenzoate in Highly Alkaline Media. Curvature in the khyd vs Profile
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The hydrolyses of phthalide (2a) and thiophthalide (3) have been studied in highly alkaline media, T = 25 deg C, μ = 3 (KCl).For both esters, an upward curvature in the plot of khyd vs is observed, suggestive of the onset of a second order in process in the hydrolysis.Carbonyl 18O-exchange studies indicated that no 18O is lost from the ester recovered from the hydrolysis media at times up to 3t1/2 hydrolysis.Solvent kinetic isotope (skie) studies indicate that for 3, (khyd)H2O/D2O is inverse throughout the entire range of .The lack of 18O-exchange and the inverse nature of the skie on khyd suggest that the curvature in the khyd vs plots is not due to the involvement of two hydroxides in the hydrolytic process.A correlation of the khyd data with the acidity function H- appropriate for highly alkaline media is linear and suggests the involvement of a single hydroxide throughout the entire range.A reinvestigation of the alkaline hydrolysis of methyl o-methoxybenzoate (4) accompanied by 18O-exchange studies failed to detect unambiguous evidence for a bona fide second order in process.
- Kellogg, B. A.,Brown, R. S.,McDonald, R. S.
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p. 4652 - 4658
(2007/10/02)
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- Flash Vacuum Pyrolysis of Sulfinyl Stabilised Phosphorus Ylides: Generation and Reactivity of Sulfinylcarbenes
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Flash vacuum pyrolysis of α-alkanesulfinyl phosphorus ylides results mainly in extrusion of Ph3P to give thioesters, presumably by 1,2-oxygen transfer in the initially formed sulfinyl carbenes; for α-arenesulfinyl ylides loss of Ph3PO to give additional products is also observed.
- Aitken, R. Alan,Drysdale, Martin J.,Ryan, Bruce M.
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p. 1699 - 1700
(2007/10/02)
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- Conversion of Amides to S-Alkyl and S-Aryl Thioesters via Nitrosoamides and Nitroamides
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Thiolates react at room temperature with nitrosoamides and, even more rapidly, with nitroamides to afford good yields of S-alkyl and S-aryl thioesters; by-products arising from N-to-S transnitrosations and transnitrations are practically not observed.
- Berenguer, Ramon,Garcia, Jordi,Vilarrasa, Jaume
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p. 305 - 306
(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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- A Formylcarbonium Ion Synthon. Synthesis of 3-Thio-Substituted 2-Amino Acids and Thio-Substituted Enamines from 2-Acyloxyacrylonitriles
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The utilization of 2-acyloxy-3-phenylthiopropionitriles (2) which were prepared by the Michael addition of thiophenol to 2-acyloxyacrylonitriles (CH2=C(CN)OCOR), as a formylcarbonium ion synthon, was demonstrated by the transformation of 2 into S-phenylcysteine and 2-phenylthio enamines.
- Oku, Akira,Hori-ie, Naofumi,Harada, Toshiro
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p. 609 - 612
(2007/10/02)
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- THIOALKYLTRIBUTYL- AND THIOALKOXYTRIPHENYLPHOSPHONIUM SALTS: PREPARATION AND APPLICATION TO THE SYNTHESIS OF THIOLESTERS AND UNSYMMETRICAL SULFIDES
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Thioalkoxyphosphonium salts, Ph3PSR(1+)*ClO4(1-) (3) and Bu3PSR(1+)*X(1-) (X=ClO4 and BF4) (5), have been prepared from the corresponding tertiary phosphines and disulfides by simple procedures, which involve (i) constant current electrolysis in acetonitrile in the presence of either HClO4 (for 3) or PhCOOH and LiX (for 5), and (ii) stirring an equimolar mixture of a phosphine, a disulfide, PHCOOH, and LiX in acetonitrile at ambient temperature.For the preparation of 3, which have been reported as useful reagents for the synthesis of unsymmetrical disulfides, the electrochemical method is recomended, while for 5 the latter non-electrochemicl procedure gave better results.Reactions of the phosphonium salts 5 with carboxylic acidsand primary alcohols in benzene at ambient temperature gave thiolesters and unsymmetrical sulfides, respectively, in fair to excellent yields.Keywords - triphenylphosphine; tributylphosphine; disulfide; thioalkoxyphosphonium salt; thiolester; unsymmetrical sulfide
- Ohmori, Hidenobu,Maeda, Hatsuo,Konomoto, Kohichi,Sakai, Kiyoshi,Masui, Masaichiro
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p. 4473 - 4481
(2007/10/02)
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- Synthesis and Application of Imidazole Derivatives. Synthesis and Acyl Activation of 2-Acyl-1-methyl-1H-imidazoles
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2-Acyl-1-methyl-1H-imidazoles (3) were prepared in good yields by treating 1-acylpyrrolidines (5) with 2-lithio-1-methyl-1H-imidazole (2) at -78 deg C.The acyl group of 3 was very stable under various severe conditions, but 2-benzoylimidazole (3a) was gradually hydrolyzed by heating with 1.3 N NaOH to produce benzoic acid and 1-methyl-1H-imidazole.Acyl activation of 3 was performed by direct quaternization of 3 with iodomethane or dimethyl sulfate or more successfully by quaternization of the corresponding O-trimethylsilylated gem-cyanohydrin (11) with dimethyl sulfate.Keywords- acylimidazole; 2-acylimidazole; imidazolium salt; acyl group activation; acylation; C-C bond fission; protecting group; latent functionality
- Ohta, Shunsaku,Hayakawa, Satoshi,Moriwaki, Hiroki,Harada, Suzumi,Okamoto, Masao
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p. 4916 - 4926
(2007/10/02)
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- Thioimidate N-Oxides: Nitrones of Thio Esters
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A group of three C-phenyl and three C-alkyl thioimidate N-oxides (nitrones of thio esters) was prepared by S-alkylation of N-alkylthiohydroxamic acids with methyl or ethyl iodide followed by basification of the resulting hydroiodide salts.An X-ray crystallographic analysis of S-methyl N-Methylthiobenzimidate N-oxide (9Z) established the Z stereochemistry for the more stable isomer.The 1H NMR, 13C NMR, IR, and UV spectral properties of the thio ester nitrones are reported.The E/Z stereochemistry of the C-alkyl derivatives is tentatively assigned on the basis of NOE measurements, long-range coupling, and chemical shift correlations.Thermal equilibration in bromobenzene-d5 at 80 deg C gave the following E/Z ratios: C-phenyl, 5:95; C-methyl, 46:54; C-ethyl, 53:47; C-isopropyl, 83:17.The equilibrium values are rationalized in terms of a balance between electronic stabilization and steric destabilization of the Z isomers.Hydrolysis of 9Z in aqueous acid at 100 deg C gave S-methyl thiobenzoate and N-methylhydroxylamine, whereas basic hydrolysis at 100 deg C afforded N-methylbenzohydroxamic acid as the principal initial product.
- Coates, Robert M.,Firsan, Sharbil J.
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p. 5198 - 5209
(2007/10/02)
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- Electroreduction of Organic Compounds, 6. Electroreduction of N,N-Disubstituted Thioamides in the Presence of Electrophils
-
Electron-uptake by the N,N-disubstituted thioamides 1-4 in aprotic medium and the behaviour of their radical anions depend substantially on the nature of the thioacyl group and the nitrogen substituents as shown by polarographic and cyclovoltammetric measurements. - Good yields of the α-amino thioethers 8-13 are obtained by preparative electroreduction in the presence of alkylating agents.The corresponding α-amino-silyl thioethers 23 are further reduced to α-(trimethylsilyl)benzylamines 24.In the presence of oxygen and ethyl halide S-ethyl thiobenzoate (27) is formed from 2a or c.
- Voss, Juergen,Wiegand, Gabriele,Huelsmeyer, Karin
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p. 4806 - 4820
(2007/10/02)
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- SYNTHETIC APPLICATION OF THIOSILANES TO THIOESTERS
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Thiosilanes such as ethylthiotrimethylsilane, hexamethyldisilthiane, and t-butylthiotrimethylsilane, react readily with acyl chlorides at room temperature in the presence of potassium fluoride to give the corresponding thioesters in excellent yields.
- Ando, Wataru,Furuhata, Toshiya,Tsumaki, Hidetoshi,Sekiguchi, Akira
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p. 885 - 886
(2007/10/02)
-
- Aromatic Substitution. 46. Methyl (Ethyl) Thio(Dithio)carboxylation of Aromatics with S-Methyl (S-Ethyl) Thiocarboxonium and Dithiocarboxonium Fluoroantimonates
-
S-Methyl(S-ethyl)thio(dithio)carboxinium ions were prepared by reacting methyl(ethyl) fluoride-antimony pentafluoride with carbonyl sulfide (carbon disulfide) and studied with 1H and 13C NMR spectroscopy.The ions were subsequently used in the novel carboxylation reaction of arenes to S-methyl (S-ethyl) thio(dithio)benzoates.The method was also found to be adaptable to the carboxylation of polystyrene to poly(styrenecarboxylic acid) without degradation of the polymer backbone.
- Olah, George A.,Bruce, Mark R.,Clouet, Francoise L.
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p. 438 - 442
(2007/10/02)
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- Utilisation of Sulphur-containing Leaving Groups. Part 2. Monitored Reduction of Carboxylic Acids into Alcohols or Aldehydes via 3-Acylthiazolidine-2-thiones by Sodium Borohydride or Di-isobutylaluminium Hydride
-
3-Acylthiazolidine-2-thiones (2) have been prepared by three methods, and treated with di-isobutylaluminium hydride or sodium borohydride to give aldehyde or alcohol in high yield, respectively.The original yellow colour disappears when reduction is finished, enabling the reaction to be monitored.The high reactivity of the carbonyl group in amide (2) was briefly discussed.
- Nagao, Yoshimitsu,Kawabata, Kohji,Seno, Kaoru,Fujita, Eiichi
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p. 2470 - 2473
(2007/10/02)
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