- Air-stable binuclear Titanium(IV) salophen perfluorobutanesulfonate with zinc power catalytic system and its application to C–S and C–Se bond formation
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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
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- Visible-Light-Promoted Thiyl Radical Generation from Sodium Sulfinates: A Radical-Radical Coupling to Thioesters
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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)
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- Thioesters as Bifunctional Reagents for 2-Naphthylamine Sulfuracylation
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An efficient and convenient strategy for the preparation of diaryl sulfides via a Fe-promoted direct sulfuracylation of 2-naphthylamine using thioesters as bifunctional reagents is described. This synthetic strategy features high chemoselectivity, good substrate scope and functional group tolerance. (Figure presented.).
- Xiao, Fuhong,Yuan, Shanshan,Wang, Dahan,Liu, Saiwen,Huang, Huawen,Deng, Guo-Jun
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supporting information
p. 3331 - 3336
(2019/06/13)
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- Preparation method and application of novel ionic binuclear Schiff base titanium complex
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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.
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Paragraph 0052; 0053
(2018/04/03)
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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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- Rapid and convenient thioester synthesis under phase-transfer catalysis conditions
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Various thioesters were obtained through an efficient phase-transfer catalysis method, by treating several thiophenols with different acyl chlorides, in a biphasic system composed of 10% aqueous NaOH and dichloromethane in the presence of tetrabutylammonium chloride. The thiolation reaction was complete in only 5 minutes, at 0C. Taylor & Francis Group, LLC.
- Simion, Cristian,Hashimoto, Iwao,Mitoma, Yoshiharu,Simion, Alina Marieta,Egashira, Naoyoshi
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experimental part
p. 2480 - 2488
(2011/02/23)
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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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- A convenient one-pot synthesis of thiol esters from disulfides using a Zn/AlCl3 system
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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
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- Kinetics and mechanism of the aminolysis of aryl propanedithioates in acetonitrile
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The kinetics and mechanism of the aminolysis of aryl proanedithioates with benzylamines are investigated in acetonitrile at - 35.0 °C. A large magnitude of the Hammett (ρx and ρz) and Broensted (βx and βz) coefficients and exceptionally large cross-interaction constant ρxz(= 3.5) are consistent with a stepwise mechanism in which leaving group expulsion from an intermediate, T±, is the rate-determining step. The faster rates observed for dithio esters (I1) than for thio esters (I), and the validity of the reactivity-selectivity principle (RSP) are also in line with the mechanism proposed. The kH/kD values (= 1.0-1.8) determined with deuterated benzylamines (XC6H4CH2ND2) and the activation parameters, ΔH≠(?8 kcal mol-1) and ΔS≠(= -16 to -23 e.u.), suggest that proton transfer occurs concurrently with leaving group departure in the transition state.
- Hyuck Keun Oh,Sun Kyung Kim,Hai Whang Lee,Lee
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p. 313 - 317
(2007/10/03)
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- Kinetics and mechanism of the aminolysis of thiophenyl methylacetates in acetonitrile
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The aminolysis of Z-thiophenyl methylacetates (C2H5C(double bond O)SC6H4Z) with X-benzylamines in acetonitrile has been investigated at 45 °C. The reaction is found to proceed by a stepwise mechanism in which the rate-determining step is the breakdown of the zwitterionic tetrahedral intermediate, T±, with possibly a hydrogen-bonded four-center-type transition state. These mechanistic conclusions are drawn based on (i) the large magnitude of βX (= 1.2 to approximately 2.5) and βz (= -0.9 to approximately -1.5), (ii) the normal kinetic isotope effects (kH/kD?1.2) involving deuterated benzylamines (XC6H4CH2ND2), (iii) a large positive ρxz (= 2.4) and (iv) adherence to the reactivity-selectivity principle in all cases. The extremely large βX (βnuc) values can be accounted for by the loss of a strong localized cationic charge on the N atom of benzylamines in the expulsion from the T±. The pKa° (≥10.0) is high due to a large ratio of the expulsion rates of the amine (k-a) to thiophenolate (kb) (k-a/kb) from the T±.
- Oh, Hyuck Keun,Yang, Jin Hee,Cho, In Ho,Lee, Hai Whang,Lee, Ikchoon
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p. 485 - 490
(2007/10/03)
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- Flash Vacuum Pyrolysis of Alkoxycarbonyl/Sulfinyl Stabilised Phosphorus Ylides: Generation and Intramolecular Insertion of Alkoxycarbonyl(sulfenyl)carbenes
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Flash vacuum pyrolysis of phosphorus ylides stabilised both by ester and sulfinyl groups results mainly in extrusion of Ph3PO to generate alkoxycarbonyl(sulfenyl)carbenes; these undergo intramolecular insertion into CH of the alkoxycarbonyl group giving β-lactones which under the conditions lose CO2 to afford alkenyl sulfides.
- Aitken, R. Alan,Drysdale, Martin J.,Ryan, Bruce M.
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p. 805 - 806
(2007/10/02)
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- A SIMPLE SYNTHESIS OF THIOL ESTERS FROM COPPER-I-MERCAPTIDES AND ACYL CHLORIDES
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Thiol esters are obtained from acyl chlorides and copper-I-mercaptides in excellent yields.
- Reissig, Hans-Ulrich,Scherer, Bernadette
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p. 4259 - 4262
(2007/10/02)
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