- Palladium Catalyzed Direct Carbonylative Thiomethylation of Aryldiazonium Salts and Amines with 4-(Methylthio)-2-Butanone as (Methylthio) Transfer Agent
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Herein, an interesting palladium-catalyzed procedure for the direct carbonylative thiomethylation of aromatic amine derivatives with 4-methylthio-2-butanone is developed. Using 4-methylthio-2-butanone as (methylthio) transfer agent, a variety of corresponding thioesters are obtained with moderate to good yields under base-free condition. In addition, good functional group tolerance can be observed.
- Tian, Qingqiang,Xu, Shasha,Zhang, Chiying,Liu, Xinyi,Wu, Xiangwei,Li, Yahui
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p. 8797 - 8804
(2021/07/19)
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- Palladium-catalyzed intermolecular transthioetherification of aryl halides with thioethers and thioesters
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Functional group transfer reactions are an important synthetic tool in modern organic synthesis. Herein, we developed a new palladium-catalyzed intermolecular transthioetherification reaction of aryl halides with thioethers and thioesters. The synthetic utility and practicality of this catalytic protocol are demonstrated in a wide range of successful transformations (>70 examples). This catalytic protocol is applicable in carbonylative coupling processes as well, and the first example of carbonylative methylthioesterification of aryl halides has been achieved. Notably, this work also provides an approach to using natural products, such as methionine and selenomethionine, as the functional group sources.
- Li, Yahui,Bao, Gao,Wu, Xiao-Feng
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p. 2187 - 2192
(2020/03/11)
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- Controllable phosphorylation of thioesters: Selective synthesis of aryl and benzyl phosphoryl compounds
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The controllable phosphorylations of thioesters were developed. When the reaction was catalyzed by a palladium catalyst, aryl or alkenyl phosphoryl compounds were generated through decarbonylative coupling, while the benzyl phosphoryl compounds were produced through deoxygenative coupling when the reaction was carried out in the presence of only a base.
- Xu, Kaiqiang,Liu, Long,Li, Zhaohui,Huang, Tianzeng,Xiang, Kang,Chen, Tieqiao
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p. 14653 - 14663
(2020/12/29)
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- Electrophilic Activation of Carboxylic Anhydrides for Nucleophilic Acylation Reactions
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Nucleophilic acylation of symmetrical carboxylic anhydrides has inherited limitation of reaction efficiency along with relatively poor reactivity. Traditionally, one equivalent carboxylic acid is generated during nucleophilic acylation of a symmetrical anhydride, which always limits the yield of final product to 50percent or less. This is a major drawback, which discourages the use of anhydrides for laboratory or industrial applications. Electrophilic activation of carboxylic anhydride using methanesulfonyl chloride is found to be an efficient method for nucleophilic acylation, which increases product yield by restricting the formation of corresponding acid as a side product. The developed protocol found to be a mild and high yielding methodology for one-pot nucleophilic acylation of carboxylic anhydrides with several type of N- and S-nucleophiles demonstrating appreciable functional group tolerance.
- Kumar, Varun,Kumar, Yashwant,Lal Meena, Chhuttan,Mahajan, Dinesh,Rana, Anil,Sharma, Nidhi
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p. 3902 - 3910
(2018/09/29)
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- One-pot odourless synthesis of thioesters via in situ generation of thiobenzoic acids using benzoic anhydrides and thiourea
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An efficient and odourless procedure for a one-pot synthesis of thioesters by the reaction of benzoic anhydrides, thiourea and various organic halides (primary, allylic, and benzylic) or structurally diverse, electron-deficient alkenes (ketones, esters, and nitriles) in the presence of Et3 N has been developed. In this method, thiobenzoic acids were in situ generated from the reaction of thiourea with benzoic anhydrides, which were subjected to conjugate addition with electron-deficient alkenes or a nucleophilic displacement reaction with alkyl halides.
- Abbasi, Mohammad,Khalifeh, Reza
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supporting information
p. 1265 - 1273
(2015/08/18)
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- Synthesis of β-amino-α,β-unsaturated ketone derivatives via sequential rhodium-catalyzed sulfur ylide formation/rearrangement
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In the presence of a Rh(II) catalyst and β-(methylthio)-α,β-unsaturated ketones, 1-sulfonyl-1,2,3-triazoles can be converted into functionalized β-amino-α,β-unsaturated ketones via formation of α-imino rhodium carbene/sulfur ylide and subsequent rearrangement. The products decompose to useful 2-methylthiopyrrole derivatives conveniently in high yield.
- He, Jun,Man, Zengming,Shi, Yinping,Li, Chuan-Ying
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p. 4816 - 4823
(2015/05/13)
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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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- Rhodium-catalyzed acyl-transfer reaction between benzyl ketones and thioesters: Synthesis of unsymmetric ketones by ketone CO-C bond cleavage and intermolecular rearrangement
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In the presence of catalytic amounts of RhH(CO)(PPh3) 3 and 1,2-bis(diphenylphosphino)benzene (dppBz), acyl groups were transferred between benzyl ketones and thioesters/aryl esters. The rhodium complex catalyzed the cleavage of keto
- Arisawa, Mieko,Kuwajima, Manabu,Toriyama, Fumihiko,Li, Guangzhe,Yamaguchi, Masahiko
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supporting information; experimental part
p. 3804 - 3807
(2012/09/07)
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- Identification and biosynthesis of tropone derivatives and sulfur volatiles produced by bacteria of the marine Roseobacter clade
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Bacteria of the Roseobacter clade are abundant marine bacteria and are important contributors to the global sulfur cycle. The volatiles produced by two of its members, Phaeobacter gallaeciensis and Oceanibulbus indolifex, were analyzed to investigate whether the released compounds are derived from sulfur metabolism, and which biosynthetic pathways are involved in their formation. Both bacteria emitted different sulfides and thioesters, including new natural compounds such as 5-methyl phenylethanethioate (16) and butyl methanesulfonate (21). The S-methyl alkanoates were identified by comparison with standards that were synthesized from the respective methyl alkanoates by a new method using an easily prepared aluminium/sulfur reagent. Phaeobacter gallaeciensis is also able to produce tropone (37) in large amounts. Its biosynthesis was investigated by various feeding experiments, showing that 37 is formed via a deviation of the phenylacetate catabolism. The unstable tropone hydrate 42 was identified as an intermediate of the tropone biosynthesis that was also released together with tropolone (38). The Royal Society of Chemistry 2010.
- Thiel, Verena,Brinkhoff, Thorsten,Dickschat, Jeroen S.,Wickel, Susanne,Grunenberg, Joerg,Wagner-Doebler, Irene,Simon, Meinhard,Schulz, Stefan
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experimental part
p. 234 - 246
(2010/04/29)
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- A Fast and Solvent-Free Conversion of Thioamides into Thioesters
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Solvent-free irradiation of thiomorpholides with two kinds of methylating agents under microwave or ultrasonic conditions gave the corresponding thioesters in high yield. The method is simple and avoids prolonged heating with solvents.
- Darabi, Hossein R.,Aghapoor, Kioumars,Tabar-Heidar, Kourosh
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- 1-(2,5-dichlorophenyl)-2,2-bis(methylsulfanyl)vinyl esters as highly efficient chemoselective acylating reagents
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1-(2,5-Dichlorophenyl)-2,2-bis(methylsulfanyl)vinyl esters 4f-k were prepared in yields usually greater than 90%, by reacting acyl chlorides with 1-(2,5-dichlorophenyl)-2,2-bis(methylsulfanyl)ethanone enolate. These esters were demonstrated to be excellent chemoselective reagents for the acylation of amines, alcohols, thiols, pyrrole and indole. From all the acylation reactions the dimethyl α-oxo dithioacetal 2d, recyclable for the preparation of esters 4f-k, could be recovered in 90-100% yield.
- Degani,Dughera,Fochi,Serra
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p. 1200 - 1208
(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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- REACTION OF para-SUBSTITUTED AROMATIC ACIDS WITH METHYL THIOCYANATE IN TRIFLUOROACETIC ACID
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We have investigated the reactions of aromatic carboxylic acids (p-XC6H4COOH, in which X = F, Cl, Br, I, NO2, CH3, H, OCH3) with methyl thiocyanate in trifluoroacetic acid.It was shown that the starting acids are converted to S-methyl benzothioates and the nitrile of the acid .In addition to starting acid, in the reaction mixtures products of the reaction of CF3COOH with methyl thiocyanate were identified. Keywords: methyl thiocyanate, trifluoroacetic acid, S-methyl benzothioates, methyl mercaptan.
- Polivin, Yu. N.,Karakhanov, R. A.,Vinokurov, V. A.,Silin, M. A.,Bratkov, A. A.
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p. 324 - 328
(2007/10/02)
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- Nucleophilic and Electrophilic Mercaptanylations via 2-(Trimethylsilyl)ethanethiol-Derived Reagents
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2-(Trimethylsilyl)ethanethiol reacts with carboxylic acids, alkyl halides, epoxides, and enones to provide acyl- and alkyl-substituted 2-(trimethylsilyl)ethyl sulfides.Electrophilic mercaptanylation is effected by a thiol-sulfonate reagent derived from 2-(trimethylsilyl)ethanethiol.
- Anderson, M.B.,Ranasinghe, M.G.,Palmer, J.T.,Fuchs, P.L.
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p. 3125 - 3127
(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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- ELEKTROCHEMISCHE OXIDATION VON DITHIOCARBONSAEUREESTERN ZU ISOTHIAZOLEN
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Electrolysis of alkyl arenedithioates 1 in acetonitrile with benzyl-triethyl-ammonium chloride as supporting electrolyte yields 5-aryl-4-cyano-3-methyl-isothiazoles 4.A reaction path is discussed according to which the dithioesters 1 are chlorinated at the anode and subsequently react with 3-iminobutyronitrile (6), generated at the cathode, to form the isothiazoles 4.
- Voss, Juergen,Mischke, Peter,Adiwidjaja, Gunadi
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p. 261 - 274
(2007/10/02)
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- The Preparation of (Methylthio)- and (Methylseleno)-tri(alkyl or aryl)phosphonium Salts and Their Reactions with Carboxylic Acids and Alcohols
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A series of (methylthio)- and (methylseleno)-triphenylphosphonium salts and the analogous tributylphosphonium salts have been prepared by methylation of the corresponding tertiary phosphine sulfides and selenides.Details of their 1H, 13C and 31P n.m.r. spectra are given.Whereas the (methylthio)- and (methylseleno)-triphenylphosphonium salts undergo rapid decomposition in the presence of tertiary ammonium carboxylates or tertiary amines, the (methylthio)- and (methylseleno)-tributylphosphonium salts convert such carboxylates into methanethiol and methaneselenol estersin acceptable yields.A tris(dimethylamino)(methylthio)phosphonium salt, on the other hand, converts benzoate into methyl benzoate in quantitative yield.Inferior yields of (methylthio)- and (methylseleno)-alkanes are obtained from two primary alcohols and the tributylphosphonium salts.
- Haynes, Richard K.,Indorato, Carlo
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p. 1183 - 1194
(2007/10/02)
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- Reaction of Aryl Aldehydes with Thiocyanates in the Presence of Tributylphosphine
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Aryl aldehydes react with methyl thiocyanate in the presence of tributylphosphine to afford S-methyl thiobenzoates and arylacetonitriles in good yields.This is a novel disproportionation reaction involving carbon-carbon bond formation.These compounds thus obtained are easily converted into deoxybenzoins using sodium hydride.On the other hand, p-dialkylaminobenzaldehydes react with methyl thiocyanate under the same conditions to furnish both the corresponding trans-dicyanostilbenes and succinonitriles in moderate yields.Finally, the reaction was carried out with aryl thiocyanates resulting in the formation of addition products.
- Yokoyama, Masataka,Ohteki, Hiroko,Kurauchi, Masahiko,Hoshi, Kazuko,Yanagisawa, Eizaburo,et al.
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p. 2635 - 2640
(2007/10/02)
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- SYNTHESIS OF MONO- AND 1,4-DICARBONYL COMPOUNDS BASED ON THE OXYGENATION OF PHOSPHONATE CARBANIONS. SYNTHESIS OF DIHYDROJASMONE, ALLETHRONE AND METHYLENOMYCIN B
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Oxidation of the α-alkylthio-substituted phosphonate carbanions was found to give the corresponding carbonyl compounds.A new synthesis of 1,4-dicarbonyl systems involving the oxygenation of phosphonate carbanions as a key step is described.Total synthesis of dihydrojasmone and allethrone and formal synthesis of methylenomycin B is reported.
- Mikolajczyk, Marian,Midura, Wanda,Grzejszczak, Slawomir
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p. 2489 - 2492
(2007/10/02)
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- An Odorless Preparative Method of Sulfides and Thiocarboxylic S-Esters Using 3-(Alkylthio)-1,2-benzisothiazole 1,1-Dioxide
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It was found that sodium salt of 1,2-benzisothiazole-3(2H)-thione 1,1-dioxide (thiosaccharin) readily reacted with alkyl halide affording 3-(alkylthio)-1,2-benzisothiazole 1,1-dioxide (3).Treatment of 3 with piperidine produces the corresponding alkanethiol in situ quantitatively and subsequent treatment with various electrophiles gives the corresponding sulfides and thiocarboxylic S-esters in good yields.
- Yamada, Hiroyuki,Kinoshita, Hideki,Inomata, Katsuhiko,Kotake, Hiroshi
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p. 949 - 950
(2007/10/02)
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- DIPHENYLPHOSPHINODITHIOIC ACID: A REAGENT FOR THE CONVERSION OF NITRILES TO THIOAMIDES
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Diphenylphosphinodithioic acid is a reagent useful for a sequence effecting the hydrolysis of nitriles under mild conditions.
- Benner, Steven A.
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p. 1851 - 1854
(2007/10/02)
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- Aromatic Substitution. 46. Methyl (Ethyl) Thio(Dithio)carboxylation of Aromatics with S-Methyl (S-Ethyl) Thiocarboxonium and Dithiocarboxonium Fluoroantimonates
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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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- A NOVEL DISPROPORTIONATION REACTION OF AROMATIC ALDEHYDES INVOLVING C-C BOND FORMATION
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The reaction of aromatic aldehydes with methyl thiocyanate in the presence of tributylphosphine afforded both S-methyl thiobenzoates and phenylacetonitriles via a novel disproportionation pathway involving carbon-carbon bond formation.
- Kurauchi, Masahiko,Imamoto, Tsuneo,Yokoyama, Masataka
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p. 4985 - 4986
(2007/10/02)
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- Pesticidal compositions containing phosphoric esters and divalent sulphur compounds
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Pesticidal composition comprising: a pesticidal, phosphoric ester the molecule of which has at least one alkyl group of 1 to 3 carbon atoms, 0.05 to 10% of an agent stabilizing the said ester against decomposition by protonisation, together with adjuvants characterized in that the stabilizing agent comprises at least one sulphur compound containing per molecule at least one divalent sulphur atom of which one valence is bonded to an atom chosen from sulphur, carbon, nitrogen, hydrogen, and metals capable of giving a salt, the other valence being bonded to an atom chosen from hydrogen, the carbon atom already noted, a second carbon atom, the nitrogen atom already noted, a second nitrogen atom, the metal atom already noted in the case of a metal of valence greater than one, a second atom of metal and oxygen when the first valence is not attached to an atom of hydrogen, the proportion of sulphur calculated with reference to the weight of the sulphur compound being between 5 and 99%. Process for stabilizing a phosphoric ester of which the molecule possesses at least one alkyl group containing 1 to 3 carbon atoms characterized in that there is added to the phosphoric ester or to a mixture which contains it, 0.05 to 10% calculated on the weight of the phosphoric acid ester of an agent capable of stabilizing the said phosphoric ester against protonisation and comprising at least one sulphur compound such as that defined thereupon.
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