10276-14-9Relevant academic research and scientific papers
Gold-catalyzed thioetherification of allyl, benzyl, and propargyl phosphates
Miura, Hiroki,Nishio, Hidenori,Shishido, Tetsuya,Toyomasu, Tomoya
, p. 1109 - 1116 (2022/03/02)
Gold-catalyzed thioetherification of C(sp3)-O bonds is described. The reaction of allyl phosphates and thiosilanes in the presence of gold nanoparticles supported on ZrO2 proceeded efficiently under mild reaction conditions to give the corresponding allyl sulfides in excellent yields. ZrO2-Supported gold nanoparticles showed excellent catalytic turnover and reusability. In addition, the C-O bonds of benzyl and propargyl phosphates underwent thioetherification to afford benzyl and propargyl sulfides. The reaction of an optically active benzyl phosphate proceeded with excellent chirality transfer to give a benzyl sulfide with high enantiomeric purity. Control experiments corroborated that soluble gold species were responsible for the efficient thioetherification of C-O bonds of phosphates, and characterization of the catalysts revealed that cationic gold species at the surface of gold nanoparticles supported on ZrO2 served as a source for highly active catalytic species.
Hemin Catalyzed Dealkylative Intercepted [2, 3]-Sigmatropic Rearrangement Reactions of Sulfonium Ylides with 2, 2, 2-Trifluorodiazoethane
Yan, Xiaojing,Li, Chang,Xu, Xiaofei,Zhao, Xiaoyong,Pan, Yuanjiang
supporting information, p. 2005 - 2011 (2020/05/18)
A dealkylative intercepted [2, 3]-sigmatropic rearrangement reaction of allylic sulfides with 2, 2, 2-trifluorodiazoethane (CF3CHN2) is reported, the commercially available and biocompatible catalyst hemin was found to efficiently catalyze this transformation across a diverse set of allylic sulfides with in situ generated CF3CHN2, providing excellent yields (up to 99%) under mild condition without inert gas protection. In addition, CF3CHN2 exhibited unique reactivity toward this process compared with other frequently used diazo reagents. This work expands the range of carbene-mediated transformations catalyzed by hemin and introduces a concise and general strategy for exploiting new possibility of reactions concerning organosulfides. (Figure presented.).
Nanolayered cobalt-molybdenum sulphides (Co-Mo-S) catalyse borrowing hydrogen C-S bond formation reactions of thiols or H2S with alcohols
Corma, Avelino,Sorribes, Iván
, p. 3130 - 3142 (2019/03/13)
Nanolayered cobalt-molybdenum sulphide (Co-Mo-S) materials have been established as excellent catalysts for C-S bond construction. These catalysts allow for the preparation of a broad range of thioethers in good to excellent yields from structurally diverse thiols and readily available primary as well as secondary alcohols. Chemoselectivity in the presence of sensitive groups such as double bonds, nitriles, carboxylic esters and halogens has been demonstrated. It is also shown that the reaction takes place through a hydrogen-autotransfer (borrowing hydrogen) mechanism that involves Co-Mo-S-mediated dehydrogenation and hydrogenation reactions. A novel catalytic protocol based on the thioetherification of alcohols with hydrogen sulphide (H2S) to furnish symmetrical thioethers has also been developed using these earth-abundant metal-based sulphide catalysts.
Aqueous hemin catalyzed sulfonium ylide formation and subsequent [2,3]-sigmatropic rearrangements
Xu, Xiaofei,Li, Chang,Tao, Zhihao,Pan, Yuanjiang
supporting information, p. 1245 - 1249 (2017/08/15)
A mild hemin catalytic system for sulfonium ylide generation via a metal carbenoid and a subsequent [2,3]-sigmatropic rearrangement reaction in aqueous solvent is well-established, with the assistance of cyclodextrin (CD) and Triton X-100. The protocol displays high catalytic activity with a broad substrate scope of aryl/alkyl allyl sulfides and diazo reagents, affording homoallyl sulfide products in up to 99% yield. Notably, this catalytic system is successful for water-insoluble allyl sulfides but ineffective for allyl amines or allyl ethers. Moreover, an unprecedented cascade reaction of sulfonium ylide formation, [2,3]-sigmatropic rearrangement and C-H insertion was reported.
One-Pot Copper-Catalysed Thioetherification of Aryl Halides Using Alcohols and Lawesson's Reagent in Diglyme
Gholinejad, Mohammad
, p. 4162 - 4167 (2015/06/30)
A new protocol for the thioetherification of structurally varied alcohols with aryl halides using Lawesson's reagent, catalysed by copper(I) iodide, and using diglyme as a safe solvent was developed. Using this method, the reactions of aryl halides proceeded efficiently, and the desired sulfides were obtained in high to excellent yields. The method uses alcohols as starting materials, which is a significant advantage over methods that start from thiols. Alcohols are widely commercially available in a much greater structural diversity than thiols, and they are also nontoxic and not foul-smelling. A reaction mechanism was proposed. A copper-catalysed method for the thioetherification of alcohols with aryl halides using Lawesson's reagent was developed.
Expanding the horizon of intermolecular trapping of in situ generated α-oxo gold carbenes: Efficient oxidative union of allylic sulfides and terminal alkynes via C-C bond formation
Li, Jiabin,Ji, Kegong,Zheng, Renhua,Nelson, Jonathan,Zhang, Liming
supporting information, p. 4130 - 4133 (2014/04/03)
With a new P,S-bidentate phosphine as the ligand to gold(i), the α-oxo gold carbenes generated in situ via gold-catalyzed intermolecular oxidation of terminal alkynes were effectively trapped by various allylic sulfides, resulting in the formation of α-aryl(alkyl)thio-γ,δ- unsaturated ketones upon facile [2,3]sigmatropic rearrangements. This journal is the Partner Organisations 2014.
Enantioselective allylic thioetherification: The effect of phosphoric acid diester on iridium-catalyzed enantioconvergent transformations
Roggen, Markus,Carreira, Erick M.
supporting information; experimental part, p. 8652 - 8655 (2012/10/08)
You'll take the high road and I'll take the low road: Enantioenriched allylic thioethers have been synthesized from chiral racemic allylic alcohols. The combination of an Ir-(P,alkene) complex and dibutyl phosphoric acid are required to attain high select
Catalytic activation of diazo compounds using electron-rich, defined iron complexes for carbene-transfer reactions
Holzwarth, Michael S.,Alt, Isabel,Plietker, Bernd
supporting information; experimental part, p. 5351 - 5354 (2012/07/14)
Carbene transfer: The electron-rich iron complex Bu4N[Fe(CO) 3(NO)] efficiently catalyzes different carbene-transfer reactions. Various diazo compounds can be used. The high stability of the employed iron complexes is demonstrated by the generation of the diazo reagent in situ and a sequential iron-catalyzed allylic sulfenylation/Doyle-Kirmse reaction. Copyright
Allylic activation across an Ir-Sn heterobimetallic catalyst: Nucleophilic substitution and disproportionation of allylic alcohol
Chatterjee, Paresh Nath,Roy, Sujit
experimental part, p. 3776 - 3785 (2012/07/14)
A nucleophilic substitution of allylic alcohols with carbon (arene, heteroarene, allyltrimethylsilane, and 1,3-dicarbonyl compound), sulfur (thiol), oxygen (alcohol), and nitrogen (sulfonamide) nucleophiles has been demonstrated using an in house developed [Ir(COD)(SnCl3)l(μ-Cl)]2 heterobimetallic catalyst in 1,2-dichloroethane to afford the corresponding allylic products in moderate to excellent yields. In 4-hydroxycoumarin, allylation occurs at the 3-position. The diaryl-substituted allylic alcohols undergo disproportionation in presence of the heterobimetallic catalyst to provide the corresponding alkenes and chalcones. An electrophilic mechanism is proposed from Hammett correlation study.
TAPC-catalyzed synthesis of thioethers from thiols and alcohols
Bahrami, Kiumars,Khodaei, Mohammad Mehdi,Khodadoustan, Nayere
experimental part, p. 2206 - 2210 (2011/10/09)
A new synthesis of thioethers is described. The reaction of aryl alcohols with aryl, heteroaryl, and alkyl thiols in the presence of TAPC as an efficient catalyst affords good to excellent yields of thioethers. Furthermore, the reaction proceeds under metal-free and solvent-free conditions thus represents an interesting complement to known methods for thioether synthesis. A plausible mechanism for this reaction is delineated. Georg Thieme Verlag Stuttgart · New York.
