- Method for synthesizing thioester through cross-coupling of visible light-catalyzed sodium sulfinate and acyl chloride
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The method takes sodium sulfinate and acyl chloride as raw materials and utilizes 2, 6 - dimethyl -1, 4 - dihydro -3, 5 - pyridine dicarboxylic acid diethyl ester and an organic alkali catalytic system to cross-couple sulfur radicals and acyl radicals und
- -
-
Paragraph 0028-0031
(2021/09/11)
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- Methanesulfonic anhydride-promoted sustainable synthesis of thioesters from feedstock acids and thiols
-
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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- Air-stable binuclear Titanium(IV) salophen perfluorobutanesulfonate with zinc power catalytic system and its application to C–S and C–Se bond formation
-
An air-stable μ-oxo-bridged binuclear Lewis acid of titanium(IV) salophen perfluorobutanesulfonate [{Ti(salophen)H2O}2O][OSO2C4F9]2 (1) was successfully synthesized by the reaction of TiIV(salophen)Cl2 with AgOSO2C4F9 and characterized by techniques such as IR, NMR and HRMS. This complex was stable open to air over a year, and exhibited good thermal stability and high solubility in polar organic solvents. The complex also had relatively strong acidity with a strength of 0.8 Ho ≤ 3.3, and showed high catalytic efficiency towards various C–S and C–Se bond formations in the presence of zinc power. This catalytic system affords a mild and efficient approach to synthesis of thio- and selenoesters, α-arylthio- and seleno-carbonyl compounds, and thio- and selenoethers.
- Wang, Lingxiao,Qiao, Jie,Wei, Jiancong,Liang, Zhiwu,Xu, Xinhua,Li, Ningbo
-
-
- Controllable phosphorylation of thioesters: Selective synthesis of aryl and benzyl phosphoryl compounds
-
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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- Tunable aryl imidazolium recyclable ionic liquid with dual br?nsted-lewis acid as green catalyst for friedel-crafts acylation and thioesterification
-
Unique tunable aryl imidazolium ionic liquids successfully catalyzed Friedel-Crafts acylation and thioesterification in sealed tubes. These reactions can form a C-C bond and a C-S bond with high atom economy. Ionic liquids exhibited high activity and catalyzed essential reactions with good to excellent yields while retaining their catalytic activities for recycling.
- Chen, Wen-Tin,Chou, Shih-Huan,Ho, Wen-Yueh,Hung, Ming-Wei,Lin, Michelle,Lin, Wesley,Lin, Yi-Jyun,Luo, Shun-Yuan,Reddy, Daggula Mallikarjuna,Thul, Mayur,Wu, Hsin-Ru,Wu, Yao-Peng
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- Metal-free thioesterification of amides generating acyl thioesters
-
A base-initiated thioesterification of amides with various thiols is reported. This reaction can take place efficiently under metal-free and air-atmospheric conditions, and provides a facile and practically useful approach to the synthesis of valuable acy
- Wang, Qun,Liu, Long,Dong, Jianyu,Tian, Zhibin,Chen, Tieqiao
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supporting information
p. 9384 - 9388
(2019/06/21)
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- Controlled Ni-catalyzed mono- and double-decarbonylations of α-ketothioesters
-
A method for Ni-catalyzed controlled decarbonylation of α-ketothioesters is described. Mono- and double-decarbonylations, which gave thioesters and thioethers, respectively, were selectively achieved by changing the ligand. A fundamental study of Ni-catalyzed decarbonylation of α-ketothioesters is presented.
- Zheng, Zhao-Jing,Jiang, Cheng,Shao, Peng-Cheng,Liu, Wen-Fei,Zhao, Tian-Tian,Xu, Peng-Fei,Wei, Hao
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p. 1907 - 1910
(2019/05/02)
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- Na2CO3-promoted thioesterification via N–C bond cleavage of amides to construct thioester derivatives
-
A mild, efficient, and transition-metal-free catalytic strategy is developed to construct thioesters via selective N–C bond cleavage of Boc2-activated primary amides. This strategy is successfully carried out with stoichiometric Na2C
- Tao, Jiasi,Yu, Weijie,Luo, Jin,Wang, Tao,Ge, Wanling,Zhang, Ziwei,Yang, Bingjie,Xiong, Fei
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p. 486 - 492
(2019/11/03)
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- Visible-Light-Promoted Thiyl Radical Generation from Sodium Sulfinates: A Radical-Radical Coupling to Thioesters
-
A convenient visible-light photoredox catalysis has been developed for the synthesis of thioesters from two readily available starting materials: acid chlorides and sodium sulfinates. The facile generation of acyl radical species under the visible light photoredox conditions allows the formation of thiyl radical species from sodium sulfinates via multiple single electron transfer reactions, where the final acyl radical-thiyl radical coupling has been accomplished. The direct radical-radical coupling strategy offers a mild and controlled photochemical approach to important synthetic building blocks such as thioesters.
- Bogonda, Ganganna,Patil, DIlip V.,Kim, Hun Young,Oh, Kyungsoo
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supporting information
p. 3774 - 3779
(2019/05/24)
-
- Preparation method and application of novel ionic binuclear Schiff base titanium complex
-
The invention provides a preparation method of a novel ionic binuclear Schiff base titanium complex and a synthetic method of applying the novel ionic binuclear Schiff base titanium complex to catalyze zinc powder and reduce disulfide or selenide to prepare sulfo(seleno) ester and dissymmetric sulfoether(selenide). The complex is a cationic binuclear Schiff base titanium complex, wherein titaniumatoms are bridged by oxygen atoms and are coordinated with a Schiff base ligand and a hydrone, and an ionic bond is formed by a cation part and an anion part of whole Schiff base titanium. The ionic binuclear Schiff base titanium complex is used as a catalyst, the zinc powder is used as a reducer, the disulfide(selenide) can be reduced and fractured, and the disulfide(selenide) can further and respectively react with anhydride, an alpha-bromo carbonyl compound and bromoalkane to prepare the sulfo(seleno) ester and the dissymmetric sulfoether(selenide). According to the preparation method provided by the invention, the defects that traditional lewis acid halide is deliquescent, an absolute solvent is used, conditions are strict and the like are overcome; an effective path for reducing the disulfide or selenide to prepare the sulfo(seleno) ester and the dissymmetric sulfoether(selenide) is provided, and the preparation method has the advantages of high yield, simpleness in operation andthe like.
- -
-
Paragraph 0048; 0049
(2018/04/03)
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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
-
supporting information
p. 1875 - 1878
(2017/04/21)
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- Mechanochemically-assisted solid-state photocatalysis (MASSPC)
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In this proof-of-concept study, we demonstrate the first successful transfer of transition metal-free photocatalysis from the conventional solution environment into the solid state, which is enabled by simultaneous irradiation with visible light and mecha
- ?trukil, Vjekoslav,Sajko, Igor
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supporting information
p. 9101 - 9104
(2017/08/18)
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- A synthesis of biaryl ketones via the C–S bond cleavage of thiol ester by a Cu/Ag salt
-
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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- Ligand-Controlled Divergent Cross-Coupling Involving Organosilicon Compounds for Thioether and Thioester Synthesis
-
A divergent cross-coupling for both thioether and thioester construction from organosilicon compounds has been developed. Predominant selectivity for Hiyama-type coupling and C1 insertion reaction was achieved under the guidance of ligands. Thioether was obtained under ligand-free conditions in which disulfide generated from homocoupling could be prevented. Meanwhile, application of bidentate phosphine ligands under carbon monoxide atmosphere (CO balloon) afforded the thioester with little decomposition, which was revealed through interval NMR tracking.
- Qiao, Zongjun,Jiang, Xuefeng
-
supporting information
p. 1550 - 1553
(2016/05/02)
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- One for Many: A Universal Reagent for Acylation Processes
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This work describes acylation reactions facilitated by a type of heterocycle-based acyl transfer agent, 2-acyloxypyridazinone. Reactions of 2-acyloxypyridazinone with carboxylic acids yield mixed carbonic anhydride intermediates, which are reactive and could be coupled with a wide range of substrates including acids, amines, alcohols, and thiols. The wide substrate scope, ease of operation (no additive or catalyst), storage and handling stability, and atom-efficiency from recycling the heterocycle carrier make the reported acylating agent attractive for acylation-based coupling reactions.
- Moon, Hyun Kyung,Sung, Gi Hyeon,Kim, Bo Ram,Park, Jong Keun,Yoon, Yong-Jin,Yoon, Hyo Jae
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supporting information
p. 1725 - 1730
(2016/06/09)
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- Direct oxidative coupling of thiols and benzylic ethers via C(sp3)-H activation and C-O cleavage to lead thioesters
-
An unprecedented C-S formation method via direct oxidative C(sp3)-H bond functionalization and C-O cleavage of benzylic ethers was developed. Various thioesters including thioester structure containing drug intermediates could be achieved by th
- Feng,Lv,Lu,Cai
-
supporting information
p. 677 - 681
(2015/02/19)
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- Catalyst-free direct decarboxylative coupling of α-keto acids with thiols: a facile access to thioesters
-
A novel, efficient, and catalyst-free strategy has been initially developed for the construction of thioesters via the direct radical oxidative decarboxylation of α-keto acids with thiols, and the corresponding target products were obtained in moderate to good yields. It offers an alternative approach for the synthesis of useful diverse thioesters.
- Yan, Kelu,Yang, Daoshan,Wei, Wei,Zhao, Jing,Shuai, Yuanyuan,Tian, Laijin,Wang, Hua
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p. 7323 - 7330
(2015/07/01)
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- Iron-catalyzed thioesterification of methylarenes with thiols in water
-
An iron-catalyzed coupling reaction of methylarenes with thiols leading to thioesters has been developed. The reactions were carried out in water with tert-butyl hydroperoxide (TBHP) as the oxidant and polyoxyethanyl α-tocopheryl sebacate (PTS) as the sur
- Wang, Liang,Cao, Jing,Chen, Qun,He, Ming-Yang
-
supporting information
p. 7190 - 7193
(2015/01/16)
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- Selective approach to thioesters and thioethers via sp3 C-H activation of methylarenes
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Novel C-S cross-dehydrogenative coupling (CDC) approaches for the selective synthesis of thioesters and thioethers have been developed via sp3 C-H activation of methylarenes and subsequent functionalization. The reaction of methylarenes with thiols resulted in thioesters in the presence of a FeBr2/TBHP system, while treatment of methylarenes with thiols in the Pd(OAc)2/O2/TBHP system led to the formation of thioethers. Both the green protocols demonstrate good functional group tolerance and satisfactory yields. This journal is
- Feng,Lu,Cai
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p. 54409 - 54415
(2015/01/16)
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- Iron-catalyzed synthesis of thioesters from thiols and aldehydes in water
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The preparation of thioesters through the iron-catalyzed coupling reaction of thiols with aldehydes is described. The reactions were carried out by using tert-butyl hydroperoxide (TBHP) as an oxidant and water as a solvent in most cases. This system is co
- Huang, Yu-Ting,Lu, Shao-Yi,Yi, Chih-Lun,Lee, Chin-Fa
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p. 4561 - 4568
(2014/06/09)
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- Metal-free cross-coupling reaction of aldehydes with disulfides by using DTBP as an oxidant under solvent-free conditions
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A DTBP-promoted C-H thiolation of aldehydes with disulfides under metal-free and solvent-free conditions is described. The system shows good functional group tolerance to afford thioesters in moderate to excellent yields. the Partner Organisations 2014.
- Zeng, Jing-Wen,Liu, Yi-Chen,Hsieh, Ping-An,Huang, Yu-Ting,Yi, Chih-Lun,Badsara, Satpal Singh,Lee, Chin-Fa
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p. 2644 - 2652
(2014/05/06)
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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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- 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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- An approach to the synthesis of thioesters and selenoesters promoted by rongalite?
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Rongalite? promotes cleavage of diaryldisulfides generating the corresponding chalcogenolate anions that then undergo facile reaction with N-acylbenzotriazoles in the presence of K2CO3 to afford thioesters in good to excel
- Lin, Shao-Miao,Zhang, Ji-Lei,Chen, Jiu-Xi,Gao, Wen-Xia,Ding, Jin-Chang,Su, Wei-Ke,Wu, Hua-Yue
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experimental part
p. 1616 - 1620
(2010/11/17)
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- Air-stable, cationic, Lewis acid, titanocene perfluorooctanesulfonate- catalyzed reductive cleavage of S-S bond by zinc and its application in synthesis of thioesters
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Titanocene perfluorooctanesulfonate is air-stable complex. In the presence of 10mol% of the complex, reductive cleavage of an S-S bond by zinc in commercial tetrahydrofuran at room temperature led to nucleophilic sulfur anion species, which reacted with acid anhydrides to afford thioesters in good to excellent yields. Copyright
- Qiu, Ren Hua,Xu, Xin Hua,Li, Yin Hui,Shao, Ling Ling,Zhang, Guo Ping,An, De Lie
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experimental part
p. 3309 - 3314
(2010/12/24)
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- Silica-promoted facile synthesis of thioesters and thioethers: A highly efficient, reusable and environmentally safe solid support
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An efficient, mild and rapid procedure for the acylation and alkylation of aromatic and aliphatic thiols mediated on a silica gel surface at room temperature is described. The protocol allows the protection of thiols under neutral heterogeneous conditions without requiring any bases or Lewis acids, and the silica gel used as the promoter can be recycled for several runs without any loss of activity.
- Basu, Basudeb,Paul, Susmita,Nanda, Ashis K.
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experimental part
p. 767 - 771
(2010/09/05)
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- Rhodium-catalyzed interconversion between acid fluorides and thioesters controlled using heteroatom acceptors
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A rhodium complex catalyzed the equilibrium acyl transfer reaction between acid fluorides and thioesters. In the presence of fluoride or thiolate acceptors, the reaction could be shifted to either product. RhH(PPh 3)4-dppe catalyzed the reaction of acid fluorides and diorgano disulfides in the presence of triphenylphosphine giving thioesters, which was accompanied by triphenylphosphine difluoride. The same complex catalyzed the reaction of aryl thioesters and hexafluorobenzene giving acid fluorides, which was accompanied by 1,4-di(arylthio)-2,3,5,6- tetrafluorobenzenes.
- Arisawa, Mieko,Yamada, Toru,Yamaguchi, Masahiko
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supporting information; experimental part
p. 6090 - 6092
(2011/01/04)
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- Palladium-catalyzed thiocarbonylation of iodoarenes with thiols in phosphonium salt ionic liquids
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(Chemical Equation Presented) Trihexyl(tetradecyl)phosphonium hexafluorophosphate, a phosphonium salt ionic liquid (PSIL) is a particularly effective general reaction media for the Pd-catalyzed carbonylation reaction of iodoarenes and thiols to form thioesters. Recycling of the ionic liquid containing active Pd-catalyst was also demonstrated.
- Cao, Hong,McNamee, Laura,Alper, Howard
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p. 3530 - 3534
(2008/09/20)
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- KF/Al2O3 catalysed synthesis of thiol esters from N-acylphthalimides and thiols
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A new method for the preparation of thiol esters from N-acylphthalimides and thiols in the presence of KF/Al2O3 is introduced.
- Movassagh, Barahman,Zakinezhad, Yousef
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p. 369 - 370
(2007/10/03)
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- Effect of modification of the electrophilic center on the α effect
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We report on a nucleophilic study of esters R-C(=X)-Y-Ar in which the electrophilic center has been modified by replacing O by S in the leaving group or carbonyl center: 4-nitrophenyl acetate (1), S-4-nitrophenyl thioacetate (2), 4-nitrophenyl benzoate (3), and O-4-nitrophenyl thionobenzoate (4). The studies include O- and S- nucleophiles as well as α nucleophiles in H2O at 25.0 ± 0.1°C. The sulfur nucleophile (4-chlorothiophenoxide, 4-ClPhS-) exhibits significant enhanced reactivity for the reactions with thiol and thione esters 2 and 4 compared with their oxygen analogues 1 and 3. On the contrary, the common nucleophile OH- is much less reactive towards 2 and 4 compared with 1 and 3. The effect of changing both the electrophilic center and the nucleofugic center on the reactivity of the other oxygen nucleophiles is not so significant: 4-chlorophenoxide (4-ClPhO-) is four to six times more reactive in the reactions with thiol and thione esters 2 and 4 compared with their oxygen analogues 1 and 3. The α effects exhibited by butan-2,3-dione monoximate (Ox-) and HOO- are strongly dependent on the nature of the electrophilic center of the substrates, indicating that the difference in the ground-state solvation energy cannot be fully responsible for the α effect. Our results clearly emphasize the strong dependence of the α effect on the substrate structure, notably, the nature of the electrophilic center. The impact of change in the nucleofuge (1-→2) and the electrophilic center (3-→4) on reactivity indicates that anucleophiles will need to be "purpose built" for decontamination and nucleophilic degradation of specific biocides.
- Um, Ik-Hwan,Lee, Ji-Youn,Bae, Sun-Young,Buncel, Erwin
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p. 1365 - 1371
(2007/10/03)
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- CeCl3/Sm induced reductive cleavage of the S-S bond in disulfide: A novel method for the synthesis of β-thioesters, thiol-esters and alkylphenyl sulfides
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Disulfide has been reduced by cerium trichloride and samarium in tetrahydrofuran to produce samarium thiolates. The "living" species reacts smoothly with α,β-unsaturated esters(nitriles) to afford β-thioesters(nitrile) under mild and neutral conditions. The new thiolate anion also reacts with acyl halides, anhydrides and alkyl or benzyl halides to give thioesters and sulfides, respectively.
- Li, Xue,Zhang, Songlin,Zhang, Yongmin
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p. 1527 - 1529
(2007/10/03)
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- Indium(I) iodide-promoted cleavage of diaryl diselenides and disulfides and subsequent condensation with alkyl or acyl halides. One-pot efficient synthesis of diorganyl selenides, sulfides, selenoesters, and thioesters
-
Diphenyl diselenides and disulfides undergo facile cleavages by indium(I) iodide and the corresponding generated selenate and thiolate anions condense in situ with alkyl or acyl halides present in the reaction mixture. Thus, a simple, efficient, and general procedure has been developed for the synthesis of unsymmetrical diorganyl selenides, sulfides (thioethers), selenoesters, and thioesters by this one-pot reaction at room temperature.
- Ranu, Brindaban C.,Mandal, Tanmay
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p. 5793 - 5795
(2007/10/03)
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- Copper-Mediated, Palladium-Catalyzed Coupling of Thiol Esters with Aliphatic Organoboron Reagents
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Thiol esters and B-alkyl-9-BBN derivatives couple in the presence of a copper(I) carboxylate mediator and a palladium catalyst. In contrast to copper-mediated, palladium-catalyzed cross-couplings of thioorganics with boronic acids, the current coupling reaction of 9-BBN derivatives is facilitated by the addition of a base such as Cs2CO3. Under optimized conditions, a variety of thiol esters react with different B-alkyl-9-BBN derivatives giving ketones in moderate to excellent yields.
- Yu, Ying,Liebeskind, Lanny S.
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p. 3554 - 3557
(2007/10/03)
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- An improved, general procedure to S-aryl thiol esters: A new synthetic application of dry arenediazonium o-benzenedisulfonimides
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The reaction between dry arenediazonium o-benzenedisulfonimides (1) and sodium thioacetate or thiobenzoate in anhydrous acetonitrile at room temperature is an efficient and safe procedure, of general validity, for the preparation of S-aryl thiol esters. The products can be easily purified and the yields are always very high. Of the 28 considered examples, the average yield of the S-aryl thioacetates (7) was 86% and that of the S-aryl thiobenzoates (8) 88%. It was possible to recover, in good amount and from all the reactions, o-benzenedisulfonimide (9), reusable for the preparation of salts 1.
- Barbero, Margherita,Degani, Iacopo,Dughera, Stefano,Fochi, Rita
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p. 1225 - 1230
(2007/10/03)
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- Convenient synthesis of thiol esters from acyl chlorides and disulfides using Zn/AlCl3
-
Various thiol esters were prepared by condensation of acyl chlorides with disulfides in the presence of Zn/AlCl3. The advantages of this method are high yields under relatively mild conditions, simple work-up, lack of toxicity, and low costs.
- Lakouraj, Moslem M.,Movassagh, Barahman,Fadaei, Zahra
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p. 1085 - 1088
(2007/10/03)
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- A convenient one-pot synthesis of thiol esters from disulfides using a Zn/AlCl3 system
-
A novel synthetic procedure for the direct preparation of thiol esters from various disulfides and symmetrical anhydrides using a Zn/AlCl3 system is described.
- Movassagh,Lakouraj,Fadaei
-
-
- 1H, 13C and 17O NMR study of substituent effects in 4-substituted phenylthiol esters
-
The 1H and 13C NMR spectra of 4-substituted phenylthiol acetates, benzoates and cinnamates and the 17O NMR spectra of a few thiol acetates were measured. The 13C chemical shifts of C-1 of the thiol esters when correlated with appropriate substituent-induced chemical shifts (SCS) of monosubstituted benzenes reveal an enhancement of substituent effect at C-1. Several good dual substituent parameter (DSP) correlations of 13C chemical shifts with σ1 and σR parameters were obtained for the carbons para to the substituent and the carbonyl carbons of all the three series of thiol esters display inverse substituent effects, indicating π-polarization of the thiol ester functionality by the dipole of the substituent. John Wiley & Sons Ltd.
- Perumal, Subbu,Vasuki, Gnanasambandam,Vijayabaskar, Veerappan,Selvaraj, Sangavanaicker,Boykin, David W.
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p. 720 - 726
(2007/10/03)
-
- Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 13.1 Extrusion of Ph3P from sulfinyl ylides and reactivity of the resulting sulfinyl carbenes
-
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)
-
- Sulfide Oxidation and Oxidative Hydrolysis of Thioesters by Peroxymonosulfate Ion
-
Peroxymonosulfate ion, HSO5-, as OXONE, in aqueous MeCN readily converts aryl thiobenzoates, XC6H4CO*SC6H4Z (X = p-OMe, p-Me, H, p-Cl, p-CN; Z = p-OMe, p-Me, H, m-OMe, p-Cl, m-Cl, p-NO2) into carboxylic and sulfonic acids.Reactions are second order and have small substituent effects, with ρ ca. -0.6 based on ?m and ?p substituent parameters, but rates increase markedly with increasing water content in aqueous MeCN and entropies of activation are negative.The initial step is very similar to the oxidation of methyl aryl sulfides by HSO5- which has similar solvent and substituent effects.Enthalpies of activation are much lower for oxidation of the sulfides than of the corresponding esters but entropies of activation are similar.
- Bunton, Clifford A.,Foroudian, Houshang J.,Kumar, Anurag
-
-
- Polymer-supported reactions in organic synthesis: Part II-Synthesis of some sulphides
-
Thiophenoxide ions supported on Amberlite IRA-900 (chloride from) have been treated with arylalkyl halides as well as with aryl helides to get sulphides which are useful in crop protection.Isolation of pure products by simple filtration and evaporation is an important feature of this method.
- Bandgar, B. P.,Ghorpade, Pushplata K.,Shrotri, Nirupama S.,Patil, S. V.
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p. 153 - 155
(2007/10/02)
-
- 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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