- Nickel Schiff-base complexes immobilized on boehmite nanoparticles and their application in the oxidation of sulfides and oxidative coupling of thiols as novel and reusable nano organometal catalysts
-
Boehmite nanoparticles were prepared by very simple and inexpensive procedure in water at room temperature using commercially available materials. Two Schiff-base complexes of nickel have been immobilized on the boehmite nanoparticles. These catalysts were characterized by FT-IR spectroscopy, TGA, XRD, BET, UV-DRS, TEM, SEM, EDS and ICP-OES techniques. These compounds were applied as catalysts for the oxidation of sulfides to sulfoxides and oxidative coupling of thiols to disulfides under mild reaction conditions at room temperature. These catalysts were recovered by simple filtration and reused several times without significant loss of their catalytic efficiency.
- Ghorbani-Choghamarani, Arash,Tahmasbi, Bahman,Arghand, Fatemeh,Faryadi, Sara
-
-
Read Online
- Copper-catalyzed chalcogenation of aryl iodides via reduction of chalcogen elements by aluminum or magnesium
-
Aluminum-induced copper-catalyzed coupling of aryl iodides with selenium or sulfur element could afford the corresponding diaryl selenides or sulfides in good yields. When magnesium chloride as an additive was employed, diaryl monoselenides and monosulfides were selectively obtained. On the contrary, the use of sodium carbonate produced diaryl diselenides and disulfides. The preparation of diaryl diselenides was necessary for magnesium as a reductant. Regrettably, tellurium was very low reactivity.
- Taniguchi, Nobukazu
-
p. 10510 - 10515,6
(2012)
-
Read Online
- An efficient and convenient method for preparation of disulfides from thiols using air as oxidant catalyzed by Co-Salophen
-
Disulfides have been synthesized by oxidation of thiols using air as oxidant catalyzed by Co-Salophen with high yields, mild and neutral conditions, and easy procedures of the catalyst. The products were confirmed by 1H NMR and IR.
- Chai, Pin Ji,Li, Yong Shu,Tan, Cheng Xia
-
-
Read Online
- Heterogeneously Ni-Pd nanoparticle-catalyzed base-free formal C-S bond metathesis of thiols
-
This study rationally designed a heterogeneously catalyzed system (i.e., using Ni-Pd alloy nanoparticles supported on hydroxyapatite (Ni-Pd/HAP) under an H2atmosphere) achieving an efficient base-free formal C-S bond metathesis of various thiolsviasuppression of the Ni catalysis deactivation.
- Mitamura, Kanju,Yatabe, Takafumi,Yamamoto, Kidai,Yabe, Tomohiro,Suzuki, Kosuke,Yamaguchi, Kazuya
-
-
Read Online
- Oxidation in fluoro alcohols: Mild and efficient preparation of disulfides from thiols
-
Quantitative oxidative conversion of thiols to disulfides was effected by aqueous 30% H2O2 in trifluoroethanol at ambient temperature under neutral conditions.
- Kesavan, Venkitasamy,Bonnet-Delpon, Daniele,Begue, Jean-Pierre
-
-
Read Online
- Fe3O4@S-ABENZ@VO: Magnetically separable nanocatalyst for the efficient, selective and mild oxidation of sulfides and oxidative coupling of thiols
-
Oxovanadium(IV) immobilized on Fe3O4@S-ABEN is reported as a highly efficient nanocatalyst for the oxidation of sulfides and oxidative coupling of thiols (using H2O2 as green oxidant), the products of which are obtained in high to excellent yields. The products can be separated by a simple extraction with organic solvent and the catalyst is highly efficient, especially in terms of selectivity of desired product. The catalytic system can be recycled and reused without significant loss of catalytic activity.
- Rezaei, Somaieh,Ghorbani-Choghamarani, Arash,Badri, Rashid,Nikseresht, Ahmad
-
-
Read Online
- Flavin/I2-Catalyzed Aerobic Oxidative C–H Sulfenylation of Aryl-Fused Cyclic Amines
-
We report an aerobic oxidative C–H sulfenylation of aryl-fused cyclic amines with various thiols catalyzed by flavin/I2 for the first time. While flavin I catalyzed the C–H sulfenylation of indolines to afford 3-sulfenylindoles, flavin II enabl
- Jiang, Xinpeng,Zhao, Zongchen,Shen, Zhifeng,Chen, Keda,Fang, Liyun,Yu, Chuanming
-
-
Read Online
- Isolation of stable non cyclic 1,2-disulfoxides. Revisiting the thermolysis of S-aryl sulfinimines
-
The thermolysis of S-aryl sulfinimines is shown to generate 1,2-disulfoxides and disulfides via initial Cope elimination, dimerisation of the produced sulfenic acid to a thiosulfinate, and subsequent disproportionation of the thiosulfinate. This journal is
- Souto, José A.,Lewis, Willian,Stockman, Robert A.
-
-
Read Online
- Biomimetic methane generation and disulfide formation by catalysis with a nickel complex
-
The final metabolic process of methanogen, methane generation and simultaneous disulfide formation, is simulated by the reaction of thioanisole with a toluenethiyl radical in the presence of a nickel complex, which is generated by the photolysis of a toluenethiolato-nickel complex.
- Tada, Masaru,Masuzawa, Yoshihide
-
-
Read Online
- NEW REAGENTS 4. REDUCTION OF SULPHONYL CHLORIDES AND SULPHOXIDES WITH ALUMINIUM IODIDE
-
Aluminium iodide reduces sulphonyl chlorides to disulphides and sulphoxides to sulphides under mild conditions in acetonitrile.
- Babu, J. Ramesh,Bhatt, M. Vivekananda
-
-
Read Online
- Green preparation of disulfides from corresponding thiols by poly(4-vinylpyridinium nitrate) as recoverable and new polymeric reagent
-
Poly(4-vinylpyridinium nitrate) was found to be a recyclable and highly efficient oxidizing polymer for the oxidative coupling of a variety of aliphatic or aromatic thiols to the corresponding disulfides. Poly(4-vinylpyridinium nitrate) is an extremely mild agent, which gave no other oxidized side products.
- Ghorbani-Choghamarani, Arash,Sardari, Sara
-
-
Read Online
- Air oxidative coupling of thiols to disulfides catalyzed by Fe(III)/NaI
-
A very simple and mild reaction is described for the efficient coupling of thiols at room temperature catalyzed by Fe (III)/NaI in the presence of air.
- Iranpoor,Zeynizadeh
-
-
Read Online
- Consecutive O?S/N?S Bond Cleavage in Gold-Catalyzed Rearrangement Reactions of Alkynyl N-Sulfinylimines
-
Gold-catalyzed reactions of alkynyl N-sulfinylimines were used to produce the corresponding 2H-azirines possessing sulfenyl and acyl groups at the 3-position of the azirine ring in good to excellent yields. These reactions involved internal transfer of the sulfinyl oxygen atom to form a thiooxime intermediate tethered to an α-oxo gold carbene moiety. Subsequent insertion of the carbene into the N?S bond resulted in ring construction.
- Tashiro, Hiroki,Terada, Masahiro,Nakamura, Itaru
-
-
Read Online
- A convenient method for reductive desulfonylation of β-ketosulfones with Sm/HgCl2 system
-
The Sm/HgCl2 system reduces β-ketosulfones to the corresponding ketones in moderate to good yield under mild conditions.
- Guo, Hongyun,Zhang, Yongmin
-
-
Read Online
- Novel reductive cleavage reaction of thiobenzoates with samarium diiodide: Convenient synthesis of disulfides
-
The reductive cleavage of thiobenzoates promoted by samarium diiodide afforded various kinds of disulfides in good yields under mild and neutral conditions.
- Byung Woo Yoo,Heung Soo Baek,Sam Rok Keum,Cheol Min Yoon,Ghil Soo Nam,Sung Hoon Kim,Joong Hyup Kim
-
-
Read Online
- Practical and versatile oxidation of sulfides into sulfoxides and oxidative coupling of thiols using polyvinylpolypyrrolidonium tribromide
-
A simple and highly selective oxidation of sulfides to sulfoxides and an oxidative coupling of thiols with polyvinylpolypyrrolidoniume tribromide has been developed. A series of sulfides and thiols was oxidized selectively at room temperature in good to excellent yields.
- Ghorbani-Choghamarani, Arash,Azadi, Gouhar,Tahmasbi, Bahman,Hadizadeh-Hafshejani, Mojtaba,Abdi, Zainab
-
-
Read Online
- Fe3O4 MNPs-DETA/Benzyl-Br3: A new magnetically reusable catalyst for the oxidative coupling of thiols
-
We report a new strategy to immobilize a bromine source on the surface of magnetic Fe3O4 nanoparticles (Fe3O4 MNPs-DETA/Benzyl-Br3) leading to amagnetically recoverable catalyst, which exhibits high catalytic efficiency in oxidative coupling of thiols to the disulfides (89–98%). The Fe3O4 MNPs-DETA/Benzyl-Br3 catalyst was fabricated by anchoring 3-chloropropyltrimethoxysilane (CPTMS) onmagnetic Fe3O4 nanoparticles, followed with N-benzylation and reaction with bromine in tetrachloridecarbon. The resulting nanocomposite was analyzed by a series of characterization techniques such as FT-IR, SEM, TGA, VSM and XRD. The catalyst could be recovered viamagnetic attraction and could be recycled at least 5 times without appreciable decrease in activity.
- Shiri, Lotfi,Kazemi, Mosstafa
-
-
Read Online
- Diastereoselective Synthesis of Z-Alkenyl Disulfides from α-Thiophosphorylated Ketones and Thiosulfonates
-
We developed a simple and efficient method for the synthesis of functionalized unsymmetrical Z-alkenyl disulfides under mild conditions in moderate to good yields. The designed method is based on the reaction of α-thiophosphorylated carbonyl compounds with thiotosylates in the presence of a base. The developed method allows the preparation of unsymmetrical Z-alkenyl disulfides bearing additional hydroxy, carboxy, or ester functionalities. (Figure presented.).
- Musiejuk, Mateusz,Doroszuk, Justyna,J?drzejewski, Bartosz,Ortiz Nieto, Gregory,Marin Navarro, Marisol,Witt, Dariusz
-
-
Read Online
- H14[NaP5W30O110] as a heterogeneous recyclable catalyst for the air oxidation of thiols under solvent free conditions
-
The catalytic oxidation of thiols to the corresponding disulfides using Preyssler's catalyst H14[NaP5W30O 110] has been studied. These highly selective oxidations gave good yields of the target disulfides.
- Hekmatshoar, Rahim,Sajadi, Sodeh,Heravi, Majid M.,Bamoharram, Fatemeh F.
-
-
Read Online
- Solvent Controlled Transformation between Sulfonyl Hydrazides and Alkynes: Divergent Synthesis of Benzo[b]thiophene-1,1-dioxides and (E)-β-iodo Vinylsulfones
-
A green, efficient and controllable transformation between sulfonyl hydrazides and alkynes leading to benzo[b]thiophene-1,1-dioxides and (E)-β-iodo vinylsulfones via radical pathway has been developed. The reaction occurs rapidly in the presence of simply H2O2 and KI without the help of any transition metal. The chemoselectivity of the reaction is determined by the solvent in which the process is performed: TFE favors the cyclic product, while H2O medium generates the iodosulfonylative product. Notably, this protocol also represents the first direct approach to the aggregation-induced-emmision (AIE) active benzo[b]thiophene-1,1-dioxides from readily available sulfonyl hydrazides and alkynes in one step. (Figure presented.).
- Ma, Yue,Wang, Kun,Zhang, Dong,Sun, Peng
-
-
Read Online
- Novel reduction of sulfonyl halides to disulfides with SmI2/THF/HMPA system
-
Sulfonyl halides can be readily reduced to corresponding disulfides with SmI2/THF/HMPA system in moderate to good yields at 60°C.
- Guo,Wang,Zhang
-
-
Read Online
- Copper(I)-Promoted C-N Cross-Coupling of N-Heterocyclic Compounds with 1,2-Di(pyrimidin-2-yl) Disulfides
-
A CuTC-promoted C-N cross-coupling of 1,2-di(pyrimidin-2-yl) disulfides with N-heterocyclic compounds including indoles, triazole benzotriazole, and benzoimidazole by C-S cleavage of the disulfides is reported.
- Wei, Kai-Jie,Quan, Zheng-Jun,Zhang, Zhang,Da, Yu-Xia,Wang, Xi-Cun
-
-
Read Online
- Efficient electrosynthesis of sulfinic esters via oxidative cross-coupling between alcohols and thiophenols
-
A new protocol for S O bond formation was developed by electrochemical oxidative cross-coupling between alcohols and thiophenols. With this strategy, a series of valuable sulfinic ester derivatives were synthesized up to 96% yield from basic starting materials. A preliminary mechanistic investigation reveals that this reaction involves oxygen reduction reaction (ORR).
- Gong, Fengping,Lu, Fangling,Zuo, Lin,Wang, Qi,Li, Ru,Hu, Jiaxin,Li, Zhen,Takfaoui, Abdelilah,Lei, Aiwen
-
-
Read Online
- Iodine- and PhI(OAc)2-Mediated Multicomponent Synthesis of (E)-1,3-Diphenyl-1-butene Derivatives
-
A multicomponent reaction, promoted by molecular iodine and diacetoxyiodobenzene, for the synthesis of (E)-1,3-diphenyl-1-butene derivatives from styrene and thiophenol was developed. The attractiveness of the protocol is its ability to introduce a sulfur heteroatom without a need for an extra reaction step. The scope and limitations of the protocol are investigated.
- Marakalala, Mokgethwa B.,Kinfe, Henok H.
-
-
Read Online
- Reaction of Organic Sulfur Compounds with Hyperoxide Anion (O2-anion radical). IV. Evidence for Formation of Peroxysulfur Intermediates: Oxidation of Sulfoxides, Phosphines, and Olefins with Intermediary Peroxysulfur Species
-
Formations of peroxy-sulfenate(I), -sulfinate(II), and -sulfonate(III) as intermediates have been confirmed by stripping the peroxy oxygen with three kinds of trapping agents such as sulfoxides, phosphines, and olefins, added in the reaction systems of various organic sulfur compounds with hyperoxide anion (O2-anion radical).These sulfoxides, phosphines, and olefins were inert to O2-anion radical alone while electrophilic olefins, such as α,β-unsaturated ketones reacted readily with O2-anion radical to afford the carboxylic acid.Sulfoxides, added into the reaction system of disulfide, thiosulfinic S-ester, thiosulfonic S-ester, or sulfonyl chloride with O2-anion radical, were found to be oxidized to the sulfones with peroxysulfur intermediates formed in situ in the system.Phosphines, added into the reaction system of disulfide or sodium thiolate with O2-anion radical were also oxidized to the phosphine oxides.Not only stilbene and acenaphthylene but also chalcone and its derivatives, placed in the reactions of sulfonyl chloride, sulfinyl chloride and thiosulfonic S-ester with O2-anion radical were found to be oxidized to the corresponding epoxides.These observations suggest clearly that the intermediary peroxysulfur compounds can act as oxidizing agents which oxidize these trapping agents by the nucleophilic oxygenative oxidation.Similar intermediates were postulated and confirmed in the alkaline autoxidations of thiol and disulfide in which added phosphines and sulfoxides were also found to be oxidized to their oxides.The mechanisms of the reactions of these trapping agents with peroxysulfur intermediates are discussed.
- Oae, Shigeru,Takata, Toshikazu,Kim, Yong Hae
-
-
Read Online
- Cu-catalyzed direct C-H thiolation of electron-rich arenes with arylsulfonyl hydrazides
-
An efficient Cu-catalyzed direct C–H thiolation of electron-rich arenes with arylsulfonyl hydrazides has been developed. Various mono(or bis)-thioether products were obtained in moderate to good yields. Mechanistic studies suggest that the reaction likely proceeds through free-radical formation including arylthio radical and sulfonyl radical, while both disulfanes and sulfonothioates are the major thiolation species in this transformation.
- Chen, Lingjuan,Liu, Ping,Wu, Jianglong,Dai, Bin
-
-
Read Online
- A useful modification of the Garst-Spencer furan annulation: An improved synthesis of 3,4-substituted furans
-
The reaction of keto thioenol ether 6 with dimethylsulfonium methylide gives the isolable epoxide 7, which smoothly rearranges under thermal conditions to yield the five-membered thioacetal 8. Subsequent desulfurization/aromatization with a catalytic amount of iodine furnishes the desired furan 5 in greater than 70% overall yield.
- Kurosu, Michio,Marcin, Lawrence R.,Kishi, Yoshito
-
-
Read Online
- Synthesis of new zirconium complex supported on MCM-41 and its application as an efficient catalyst for synthesis of sulfides and the oxidation of sulfur containing compounds
-
In the present work, we report synthesis of new zirconium complex supported on mesoporous silica by anchoring of adenine on the wall of functionalized MCM-41, then reacted with ZrOCl2. The resultant MCM-41-Adenine-Zr was characterized by FT-IR, XRD, TEM, SEM, TGA, EDX, ICP and BET techniques. It was exhibited that the MCM-41-Adenine-Zr can be used as an efficient and thermally stable nanocatalyst for the oxidation of sulfides, oxidative coupling of thiols and synthesis of sulfides. Moreover, this heterogeneous catalyst can be easily recovered from the reaction mixture by simple filtration and reused for several consecutive cycles without noticeable change in its catalytic activity.
- Tamoradi, Taiebeh,Ghorbani-Choghamarani, Arash,Ghadermazi, Mohammad
-
-
Read Online
- Novel reactivity of side-on (disulfido)dicopper complexes supported by bi- and tridentate nitrogen donors: Impact of axial coordination
-
(Figure Presented) What a difference a ligand makes: A comparison of the reactivity of the two complexes shown (Cu green, S yellow, N blue, O red, F pink, C gray) has revealed new redox processes previously unseen for copper-sulfur complexes. Furthermore, intriguing supporting-ligand effects on the properties of (disulfido)dicopper cores are uncovered.
- Bar-Nahum, Itsik,York, John T.,Young Jr., Victor G.,Tolman, William B.
-
-
Read Online
- Cationic rhodium(I)/PPh3 complex-catalyzed dehydrogenation of alkanethiols to disulfides under inert atmosphere
-
A cationic rhodium(I)/PPh3 complex is an effective catalyst for dehydrogenation of primary or secondary alkanethiols to symmetrical disulfides under inert atmosphere. The dependence of reactivity on the structure of thiols is examined in detail.
- Tanaka, Ken,Ajiki, Kaori
-
-
Read Online
- Mild and highly efficient method for the oxidation of sulfides and oxidative coupling of thiols catalyzed by Fe3O4@MCM-41@VO-SPATB as efficient and magnetically recoverable nanocatalyst
-
The use of oxo vanadium complex with s-propyl-2-aminobenzothioate ligand immobilized onto functionalized magnetic nanoporous MCM-41(Fe3O4@MCM-41@VO-SPATB) as efficient and magnetically recoverable nanocatalyst for oxidation of sulfides into sulfoxides and oxidative coupling of thiols into disulfides using H2O2 as green oxidant is presented. This method provides much improved modification of oxidation reactions in terms of mild reaction conditions, short reaction time and good-to-excellent yields of products. Another important feature of this method is the ability to reuse the magnetite nanocatalyst for several times with no loss of its catalytic activity.
- Nikoorazm, Mohsen,Ghorbani, Farshid,Ghorbani-Choghamarani, Arash,Erfani, Zahra
-
-
Read Online
- Novel synthesis of 2-arylbenzothiazoles mediated by ceric ammonium nitrate (CAN): A rebuttal
-
(Matrix presented) The reported synthesis of 2-arylbenzothiazoles mediated by ceric ammonium nitrate (CAN) is irreproducible; the only products formed in this reaction are bis-(p-tolyl) disulfide and p-tolyl p-toluenethiosulfonate.
- Nair, Vijay,Augustine, Anu
-
-
Read Online
- In situ generated hypoiodous acid in an efficient and heterogeneous catalytic system for the homo-oxidative coupling of thiols
-
Supported hydrogen peroxide on polyvinylpolypyrrolidone (PVPP- -H 2O2), silica sulfuric acid (SiO2-OSO 3H) and catalytic amounts of potassium iodide (KI) was developed as a heterogeneous medium for the rapid oxidative coupling of thiols into symmetrical homodisulfides. This oxidizing system proceeds under extremely mild conditions and gives no other oxidized side products.
- Ghorbani-Choghamarani, Arash,Nikoorazm, Mohsen,Azadi, Gouhar
-
-
Read Online
- Cyclization of N-Arylacrylamides via Radical Arylsulfenylation of Carbon-Carbon Double Bonds with Sulfonyl Hydrazides
-
An unprecedented tandem radical sulfenylation/cyclization reaction of N-arylacrylamides with sulfonyl hydrazides has been developed in the presence of iodine for the selective synthesis of 3-(sulfenylmethyl)oxindoles and 3-sulfenyl-3,4-dihydroquinolin-2(1H)-ones. Preliminary mechanistic studies showed that sulfonyl hydrazides decomposed completely at an early stage to thiosulfonates and disulfides, both of which underwent tandem radical sulfenylation/cyclization with N-arylacrylamides at a late stage.
- Wang, Fu-Xiang,Tian, Shi-Kai
-
-
Read Online
- Synthesis, characterization, and catalytic application of Cr and Mn Schiff base complexes immobilized on modified nanoporous MCM-41
-
Immobilization of chromium and manganese Schiff base complexes by postgrafting of ligand then metal salts on the walls of mesoporous MCM-41 functionalized with (3-aminopropyl)triethoxysilane is described. Characterization of the resulting heterogeneous catalysts by Fourier-transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), transmission electron microscopy (TEM), X-ray diffraction (XRD) analysis, and Brunauer–Emmett–Teller (BET) techniques indicated successful grafting of these two complexes inside the nanochannels of MCM-41. The complexes were found to be efficient, selective catalysts for oxidation of various sulfides to sulfoxides and oxidative coupling of thiols to corresponding disulfides using H2O2 as oxidant at room temperature. The recycling results of these heterogeneous catalysts showed good recyclability without significant loss of activity or selectivity in successive runs, indicating that the Cr and Mn Schiff base complexes supported on nanoporous MCM-41 remained intact and the coordination environments were not altered during the reaction.
- Nikoorazm, Mohsen,Ghorbani-Choghamarani, Arash,Noori, Nourolah
-
-
Read Online
- Tetrabutylammonium Iodide Mediated Sulfenylation of Poly-substituted 1 H -Pyrazol-5-amines with Arylsulfonyl Hydrazides
-
A TBAI-mediated sulfenylation of N,3-diaryl-1-arylsulfonyl-1H-pyrazol-5-amines with arylsulfonyl hydrazides has been established, and an expanded inventory of N,5-diaryl-4-(arylthio)-1H-pyrazol-3-amines was constructed through C-S bond formation and N-S bond breaking. Mechanistic investigations suggest thiosulfonate as a key intermediate in the sulfenylation, and the detosylation is promoted by the generated arylsulfinic acid. The method is characterized by simple operating conditions, broad substrate range as well as gramscale reaction.
- He, Jing,Wei, Yueting,Li, Xuezhen,Dai, Bin,Liu, Ping
-
p. 490 - 498
(2021/10/21)
-
- Copper acetate - Iodine co-mediated thiolation of 2-arylpyridines with thiophenol
-
Copper acetate - iodine co-mediated regioselective ortho-arylthiolation of 2-arylpyridines has been accomplished with inexpensive and convenient thiophenol as the arylthiolating reagent. This protocol features excellent functional group tolerance, generat
- He, Yayun,Hou, Senpeng,Hu, Junhao
-
-
- Deoxygenative C-S Bond Coupling with Sulfinates via Nickel/Photoredox Dual Catalysis
-
The C-S bond formation from aryl halides and thiols has been well established under various catalytic systems. In this work, user-friendly sulfinates have been exploited as an efficient sulfenylating reagent in the C-S couplings through visible-light-induced photo/nickel dual catalysis under base- and external reductant-free conditions. A large number of aryl sulfide products were accessed with high selectivity and high tolerance of various functionalities.
- Deng, Guo-Jun,Huang, Huawen,Mao, Guojiang,Zhao, Feng,Zhong, Shuai,Zhou, Zhiwei
-
supporting information
p. 1865 - 1870
(2022/03/16)
-
- Copper-Catalyzed N-Directed Distal C(sp3)-H Sulfonylation and Thiolation with Sulfinate Salts
-
We herein report a selective and catalytic C(sp3)-H functionalization approach to access amines bearing organo-sulfonyl and organo-thiol groups. This reaction proceeds through a cascade process of N-radical formation, alkyl radical formation via 1,5-HAT, and C-S bond formation, thereby offering a series of functionalized amines. This method could enable primary, secondary, and tertiary C(sp3)-H sulfonylation and thiolation and also exhibits good functional group tolerance.
- Chen, Guang-Le,He, Shi-Hui,Cheng, Liang,Liu, Feng
-
p. 8338 - 8342
(2021/10/25)
-
- Temperature-Controlled Chemoselective Synthesis of Thiosulfonates and Thiocyanates: Novel Reactivity of KXCN (X=S, Se) towards Organosulfonyl Chlorides
-
An efficient chemoselective protocol has been developed for the synthesis of thiosulfonates and thiocyanates by employing cost effective and commercially available organosulfonyl chlorides with potassium thio-/selenocyanate. The strategy offered the thiosulfonates and thiocyanates selectively by tuning the equivalents of KSeCN and optimizing the reaction temperature. On the other hand, thiosulfonates were obtained as sole products when organosulfonyl chlorides were treated with KSCN. Furthermore, the syntheses of diarylthioethers and aryl(heteroaryl) thioethers were carried out as a part of synthetic application of newly prepared arylthiocyanates.
- Kalaramna, Pratibha,Goswami, Avijit
-
p. 5359 - 5366
(2021/10/25)
-
- Synthesis of Symmetrical Thiosulfonates via Cu(OTf)2-Catalyzed Reductive Homocoupling of Arenesulfonyl Chlorides
-
A variety of symmetrical thiosulfonates are synthesized via Cu-catalyzed reductive homocoupling of aryl sulfonyl chlorides. This protocol uses organic amine acting as a mild reductant and low-cost copper as an effective catalyst. Such a reductive coupling process features a broad substrate scope and good functional group tolerance. Related thiosulfonate products can also be converted into diverse functional molecules.
- Liu, Lixia,Luo, Bo,Wang, Chengming
-
p. 5880 - 5883
(2021/11/27)
-
- Synthesis and Characterization of Magnetic Functionalized Ni and Cu Nano Catalysts and Their Application in Oxidation, Oxidative Coupling and Various Multi-Component Reactions
-
Abstract: Two magnetic nano catalysts of nickel and copper, Fe3O4@SiO2@DOP-BenPyr-M(II), (M=Ni and Cu) have been synthesized. These catalysts were applied as recoverable, efficient and new heterogeneous catalysts for the high yielding and room temperature one-pot procedure of selective oxidation of sulfides to sulfoxides and oxidative coupling of thiols to disulfides. In addition, the catalytic activity of Fe3O4@SiO2@DOP-BenPyr-Ni(II) was investigated as heterogeneous nanocatalyst for synthesis of 2,3-dihydroquinazolin-4(1H)-ones, 5-substituted 1H-tetrazoles and polyhydroquinolines. The synthesized catalysts were characterized by FT-IR, TGA, XRD, VSM, EDX, ICP and SEM techniques. These catalysts were recovered by an external magnet and reused several times without significant loss of catalytic efficiency. Graphic Abstract: [Figure not available: see fulltext.]
- Hajjami, Maryam,Sheikhaei, Shiva,Gholamian, Fatemeh,Yousofvand, Zakieh
-
p. 2420 - 2435
(2021/01/04)
-
- NaHSO3-Mediated Direct Synthesis of Sulfinic Esters from Sulfonyl Hydrazides under Transition-Metal-Free Conditions
-
We have developed a protocol for the NaHSO3-promoted esterification of sulfonyl hydrazides with alcohols for the synthesis of sulfinic esters. Various sulfonyl hydrazides could be converted to the corresponding sulfinic esters in good to high yields. The merits of this protocol include mild transition-metal-free reaction conditions, an inexpensive and available reagent, and operational simplicity. Controlled experiments reveal that this transformation probably undergoes via a radical pathway. (Figure presented.).
- Zhang, Guofu,Fan, Qiankun,Wang, Huimin,Zhao, Yiyong,Ding, Chengrong
-
supporting information
p. 833 - 837
(2020/12/07)
-
- Electrochemically driven synthesis of phosphorothioates from trialkyl phosphites and aryl thiols
-
A facile and elegant protocol for synthesis of phosphorothioates from trialkyl phosphites and aryl thiols via indirect electrochemical oxidation mediated by KI has been successfully developed. KI as a redox mediator, enabled the reaction of trialkyl phosp
- Guo, Xiaqun,Li, Meichao,Liu, Xin,Shen, Zhenlu,Shi, Shuxian,Wu, Zengzhi,Zhao, Lingmin
-
-
- Paired Electrolysis Enabled Ni-Catalyzed Unconventional Cascade Reductive Thiolation Using Sulfinates
-
Herein, we have reported a nickel-catalyzed cascade reductive thiolation of aryl halides with sulfinates driven by paired electrolysis. This protocol uses sulfinates as the sulfur source, and various thioethers could be synthesized under mild conditions. By mechanism exploration, we find that a cascade chemical step is allowed on the electrode interface and could alter the reaction pathway in paired electrolysis, whose findings could help the discovery of novel cascade reactions with unique reactivity.
- Kang, Jun-Chen,Li, Zi-Hao,Chen, Chao,Dong, Li-Kun,Zhang, Shu-Yu
-
supporting information
p. 15326 - 15334
(2021/10/25)
-
- Unusual Application for Phosphonium Salts and Phosphoranes: Synthesis of Chalcogenides
-
A novel strategy for the synthesis of sulfides and selenides from phosphonium salts and thio- or selenesulfonates, commercially available compounds, is described. When phosphoranes were used in the reaction, different products were obtained. The methodology does not require the use of metals, reactive species, or anhydrous conditions to be performed.
- Moura, Igor M. R.,Tranquilino, Arisson,Sátiro, Barbara G.,Silva, Ricardo O.,De Oliveira-Silva, Diogo,Oliveira, Roberta A.,Menezes, Paulo H.
-
p. 5954 - 5964
(2021/05/04)
-
- Accelerated reduction and solubilization of elemental sulfur by 1,2-aminothiols
-
Nucleophilic 1,2-aminothiol compounds readily reduce typically-insoluble elemental sulfur to polysulfides in both water and nonpolar organic solvents. The resulting anionic polysulfide species are stabilized through hydrogen-bonding interactions with the proximal amine moieties. These interactions can facilitate sulfur transfer to alkenes.
- Stoffel, Jonathan T.,Riordan, Kimberly T.,Tsui, Emily Y.
-
supporting information
p. 12488 - 12491
(2021/12/04)
-
- Iodine-catalyzed sulfuration of isoquinolin-1(2H)-ones applying ethyl sulfinates
-
An efficient sulfuration of isoquinolin-1(2H)-ones at the C-4 position is reported by employing ethyl sulfinates, and the corresponding products are obtained in moderate to excellent yields in the presence of iodine. This synthetic strategy provides a range of thioether-isoquinolin-1(2H)-ones while tolerating a number of functional groups on the isoquinoline nitrogen atom and benzene ring. In addition, pyridin-2(1H)-one is also reacted smoothly and afforded the corresponding thioether product in moderate yield. A plausible mechanism is suggested based on the preliminary mechanistic studies.
- Mu, Yangxiu,Yang, Minghua,Li, Fengxia,Iqbal, Zafar,Jiang, Rui,Hou, Jing,Guo, Xin,Yang, Zhixiang,Tang, Dong
-
p. 4934 - 4937
(2021/03/26)
-
- Iodine-Mediated Sulfenylation of Imidazo[1,2- a ]pyridines with Ethyl Arylsulfinates
-
A simple iodine-mediated approach is reported for the synthesis of sulfenylated imidazo[1,2- a ]pyridines through the reaction of imidazo[1,2- a ]pyridines with ethyl arylsulfinates under mild conditions. The reaction scope was investigated, and a plausible mechanism is proposed to elucidate the reaction process and activation mode. The results indicate that ethyl sulfinates are efficient sulfur sources for the construction of C-S bonds.
- Sun, Jian,Mu, Yangxiu,Iqbal, Zafar,Hou, Jing,Yang, Minghua,Yang, Zhixiang,Tang, Dong
-
p. 1014 - 1018
(2021/03/15)
-
- PhIO-Mediated oxidative dethioacetalization/dethioketalization under water-free conditions
-
Treatment of thioacetals and thioketals with iodosobenzene in anhydrous DCM conveniently afforded the corresponding carbonyl compounds in high yields under water-free conditions. The mechanistic studies indicate that this dethioacetalization/dethioketalization process does not need water and the oxygen of the carbonyl products comes from the hypervalent iodine reagent.
- Du, Yunfei,Ouyang, Yaxin,Wang, Xi,Wang, Xiaofan,Yu, Zhenyang,Zhao, Bingyue,Zhao, Kang
-
-
- Hydroxylamine-Derived Reagent as a Dual Oxidant and Amino Group Donor for the Iron-Catalyzed Preparation of Unprotected Sulfinamides from Thiols
-
An iron catalyzed reaction for the selective transformation of thiols (-SH) to sulfinamides (-SONH2) by a direct transfer of -O and free -NH2 groups has been developed. The reaction operates under mild conditions using a bench stable hydroxylamine derived reagent, exhibits broad functional group tolerance, is scalable and proceeds without the use of any precious metal catalyst or additional oxidant. This novel, practical reaction leads to the formation of two distinct new bonds (S=O and S?N) in a single step to chemoselectively form valuable, unprotected sulfinamide products. Preliminary mechanistic studies implicate the role of the alcoholic solvent as an oxygen atom donor.
- Chatterjee, Sayanti,Makai, Szabolcs,Morandi, Bill
-
supporting information
p. 758 - 765
(2020/11/30)
-
- Visible Light Induced Reduction and Pinacol Coupling of Aldehydes and Ketones Catalyzed by Core/Shell Quantum Dots
-
We present an efficient and versatile visible light-driven methodology to transform aryl aldehydes and ketones chemoselectively either to alcohols or to pinacol products with CdSe/CdS core/shell quantum dots as photocatalysts. Thiophenols were used as proton and hydrogen atom donors and as hole traps for the excited quantum dots (QDs) in these reactions. The two products can be switched from one to the other simply by changing the amount of thiophenol in the reaction system. The core/shell QD catalysts are highly efficient with a turn over number (TON) larger than 4 × 104 and 4 × 105 for the reduction to alcohol and pinacol formation, respectively, and are very stable so that they can be recycled for at least 10 times in the reactions without significant loss of catalytic activity. The additional advantages of this method include good functional group tolerance, mild reaction conditions, the allowance of selectively reducing aldehydes in the presence of ketones, and easiness for large scale reactions. Reaction mechanisms were studied by quenching experiments and a radical capture experiment, and the reasons for the switchover of the reaction pathways upon the change of reaction conditions are provided.
- Xi, Zi-Wei,Yang, Lei,Wang, Dan-Yan,Feng, Chuan-Wei,Qin, Yufeng,Shen, Yong-Miao,Pu, Chaodan,Peng, Xiaogang
-
p. 2474 - 2488
(2021/02/05)
-
- Unusual Deoxidative Coupling Reaction of β-Sulfinyl Esters with Benzylic Trimethylammonium Salts
-
A KOH-promoted unusual deoxidative coupling reaction of β-sulfinyl esters with benzylic trimethylammonium salts to produce thioethers is discovered for the first time. If quaternary ammonium salts synthesized from enantiomerically enriched amines are adopted, highly enantiomerically enriched benzyl thioethers (>95-99% ee) with configurations opposite to those of the enantiomerically enriched amines are obtained.
- Chen, Feng,Feng, Hang,He, Ze,Zeng, Qingle,Zhang, Qiaoling
-
p. 7806 - 7812
(2021/06/25)
-
- Nickel-Catalyzed Decarbonylative Thioetherification of Acyl Fluorides via C-F Bond Activation
-
Nickel-catalyzed decarbonylative thioetherification of acyl fluorides has been developed. This transformation allows an array of acyl fluorides to react with thiophenols. A wide range of functional groups are well tolerated and the corresponding sulfides can be obtained in good to excellent yields. This protocol provides the formation of diverse carbon-sulfur bonds via a highly efficient decarbonylative process.
- You, Jingwen,Chen, Qiang,Nishihara, Yasushi
-
supporting information
p. 3045 - 3050
(2021/05/31)
-
- Electrochemical oxidative radical cascade cyclization of olefinic amides and thiophenols towards the synthesis of sulfurated benzoxazines, oxazolines and iminoisobenzofurans
-
Heterocycles containing N and O are important structures in pharmaceuticals, agrochemicals and functional molecules. The synthesis of these compounds usually requires complex substrates and harsh reaction conditions. Herein, we introduce a mild and efficient electrochemical oxidative strategy to construct benzoxazines, oxazolines and iminoisobenzofurans without the requirement of a transition-metal catalyst and an external oxidant. In a simple undivided cell, various olefinic amides and thiophenols/diselenides react to generate 69 examples of thiolation and selenylation heterocycles in up to 83% yields. Furthermore, this radical cascade reaction provided a facile method for constructing C-S/C-Se and C-O bonds in one step.
- Alhumade, Hesham,Hu, Jianguo,Huang, Mingna,Jiang, Jianwei,Lei, Aiwen,Li, Hao,Lu, Fangling,Lu, Lijun,Ouyang, Dandan,Sun, Linghong,Wang, Ke,Xu, Jie
-
p. 7982 - 7986
(2021/11/01)
-
- Method for synthesizing thioether from thiophenol and halogenated aromatic hydrocarbon
-
The invention discloses a method for synthesizing thioether from thiophenol and halogenated aromatic hydrocarbon, and belongs to the field of organic chemistry and photocatalysis. The method uses Pd / ZnIn2 S4 As the photocatalyst, under visible light and alkaline conditions, at N. 2 The method is simple and feasible, can be carried out at room temperature, is good in yield, and has the characteristics of easy separation of the product and the catalyst in the post-treatment process.
- -
-
Paragraph 0019-0020
(2021/12/07)
-
- PdCl2/DMSO-Catalyzed Thiol-Disulfide Exchange: Synthesis of Unsymmetrical Disulfide
-
Unsymmetrical disulfides have been effectively prepared through thiol exchange with symmetrical disulfides employing a simple PdCl2/DMSO catalytic system. The given method features excellent functional group tolerance, a broad substrate scope, and operational simplicity. This reaction is especially useful for late-stage functionalization of bioactive scaffolds such as peptides and pharmaceuticals. Disulfide-containing organic dyes have also been prepared. This transformation could be extended to thiol-diselenide or thiol-ditelluride exchange affording RS-SeR′ or RS-TeR′.
- Guo, Jimin,Zha, Jianjian,Zhang, Tao,Ding, Chang-Hua,Tan, Qitao,Xu, Bin
-
supporting information
p. 3167 - 3172
(2021/05/05)
-
- Microwave-assisted and catalyst-free sulfenylation of imidazo[2,1-b]thiazoles with sulfonyl hydrazides in water
-
An efficient microwave-assisted and catalyst-free sulfenylation of imidazo[2,1-b]thiazoles with sulfonyl hydrazides has been developed in water. This method is practical and environmental friendly, and can be performed within a short reaction time. The sulfenylation reaction shows high regioselectivity, and excellent functional-group compatibility, giving the desired products in moderate to good yields.
- Wang, Shaohua,Luo, Run,Guo, Lina,Zhu, Tianxi,Chen, Xu,Liu, Wenjie
-
p. 805 - 811
(2020/07/03)
-
- An Alternative Metal-Free Aerobic Oxidative Cross-Dehydrogenative Coupling of Sulfonyl Hydrazides with Secondary Phosphine Oxides
-
An alternative metal-free, efficient and practical approach for the preparation of phosphinothioates is established via the aerobic oxidative cross-dehydrogenative coupling (CDC) of sulfonyl hydrazides with secondary phosphine oxides catalyzed by tetrabutylammonium iodide (TBAI) in the presence of atmospheric oxygen. The strategy provides an array of diverse phosphinothioates in good to excellent yields. Furthermore, two representative bioactive molecules are synthesized on up to gram scale by utilizing this method.
- Cheng, Feixiang,Liu, Jianjun,Liu, Teng,Yu, Rong,Zhang, Yanqiong
-
p. 253 - 262
(2019/12/28)
-
- CuI-catalyzed direct synthesis of diaryl thioethers from aryl boronic acids and arylsulfonyl chlorides
-
A CuI-catalyzed direct coupling of aryl boronic acids with arylsulfonyl chlorides for the preparation of diaryl thioethers was developed. The reaction is initiated by a PPh3 reduction of the arylsulfonyl chloride, followed by a CuI-catalyzed C–S coupling with an aryl boronic acid. Various arylsulfonyl chlorides can directly serve as a sulfur source in this mild and efficient reaction giving the desired products in moderate to good yields. Moreover, this practical method has also been applied to the thioetherification of aryl iodides and acetylacetones.
- Huang, Keke,Yang, Min,Lai, Xiao-Jing,Hu, Xin,Qiu, Guanyinsheng,Liu, Jin-Biao
-
-
- Nickel-Catalyzed Thiocarbonylation of Arylboronic Acids with Sulfonyl Chlorides for the Synthesis of Thioesters
-
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
-
supporting information
p. 6671 - 6676
(2020/09/02)
-
- Preparation and characterization of Cu (II) Schiff base complex functionalized boehmite nanoparticles and its application as an effective catalyst for oxidation of sulfides and thiols
-
The synthesis, characterization, and evaluation of a Schiff base Cu (II) complex functionalized boehmite nanoparticles (Cu-complex-boehmite) as a new catalyst for oxidation of sulfides and thiols in the presence of hydrogen peroxide with complete selectivity and high conversion under solvent-free and mild reaction conditions were reported. Characterization of the catalyst was performed with various physicochemical methods. This effective catalyst was evaluated in terms of activity and reusability. It indicated high catalytic activity, good recoverability and reusability, and supplied the corresponding products in high yields and short reaction times. In addition, it shows notable advantages such as simplicity of operation, heterogeneous nature, easy work up, and it could be used at least eight times with no significant loss of its activity.
- Khodaei, Mohammad Mehdi,Alizadeh, Abdolhamid,Afshar Hezarkhani, Hadis
-
-
- Synthesis and characterization of VO–vanillin complex immobilized on MCM-41 and its facile catalytic application in the sulfoxidation reaction, and synthesis of 2,3-dihydroquinazolin-4(1H)-ones and disulfides in green media
-
In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance.
- Nikoorazm, Mohsen,Khanmoradi, Maryam
-
p. 1477 - 1489
(2020/03/11)
-
- 1,1-Diphenylvinylsulfide as a Functional AIEgen Derived from the Aggregation-Caused-Quenching Molecule 1,1-Diphenylethene through Simple Thioetherification
-
An efficient and readily scalable thioetherification between 1,1-diphenylethene (DPE) and sodium arylsulfinate was developed for the synthesis of 1,1-diphenylvinylsulfide (DPVS) with the yield up to 99 %. The photophysical properties of DPVS show that the introduction of arylsulfenyl groups onto the parent molecule DPE makes DPVS a novel type of aggregation-induced emission (AIE) luminogen (AIEgen) with large Stoke's shift (up to 188 nm). These DPVS possess AIE properties due to restriction of intramolecular motions (RIM), as demonstrated by crystal structure analysis. Importantly, the AIE performance of DPVS can be applied to sense the nitroaromatic explosive picric acid in aqueous systems through a “turn-off” response.
- Wang, Bo-Wen,Jiang, Kai,Li, Jian-Xiao,Luo, Shi-He,Wang, Zhao-Yang,Jiang, Huan-Feng
-
supporting information
p. 2338 - 2343
(2020/01/24)
-
- Synthesis method of substituted thiophenol (by machine translation)
-
The invention provides a method for synthesizing substituted thiophenol, which comprises the following steps of preparing compound V compound and NaHSO3 Or KHHSO3 Reaction synthesis IV compound, compound of formula IV and SO2 Reaction-synthesis III compounds of formula III are passed NaBH in NaOH solution. 4 Of formula II is reduced and the compound of formula II is acidified to give a compound of formula I. The method for synthesizing the substituted thiophenol has the advantages of greenness, high efficiency, easiness in industrial application and the like. (by machine translation)
- -
-
Paragraph 0017; 0043; 0045; 0046
(2020/06/09)
-
- Synthetic method of diaryl disulfide compound
-
The invention relates to a synthetic method of a diaryl disulfide compound. The method comprises the following steps of: in an organic solvent, under the condition of nitrogen, using arylboronic acidand sulfur as the reaction raw materials, carrying out free radical vulcanization/self-polymerization coupling reaction under the action of a transition metal silver catalyst to obtain the diaryl disulfide compound. The method is simple in reaction condition, simple and convenient in experimental operation and high in product yield and purity, opens up a synthetic route and method for preparationof the diaryl disulfide compound, and has good application potential and research value.
- -
-
Paragraph 0026-0035; 0087-0096
(2020/11/23)
-
- S-(4-Methoxyphenyl)-4-methoxybenzenesulfonothioate as a Promising Lead Compound for the Development of a Renal Carcinoma Agent
-
Organosulfur compounds show cytotoxic potential towards many tumor cell lines. Disulfides and thiosulfonates act through apoptotic processes, inducing proteins associated with apoptosis, endoplasmic reticulum stress, and the unfolded protein response. Three p-substituted symmetric diaryl disulfides and three diaryl thiosulfonates were synthesized and analyzed for inhibition of tubulin polymerization and for human cancer cell cytotoxic activity against seven tumor cell lines and a non-tumor cell line. S-(4-methoxyphenyl)-4-methoxybenzenesulfonothioate (6) exhibited inhibition of tubulin polymerization and showed the best antiproliferative potential, especially against the 786-0 cell line, being six times more selective as compared with the non-tumor cell line. In addition, compound 6 was able to activate caspase-3 after 24 and 48 h treatments of the 786-0 cell line and induced cell-cycle arrest in the G2/M stage at the highest concentration evaluated at 24 and 48 h. Compound 6 was able to cause complete inhibition of proliferation, inducing the death of 786-0 cells, by increasing the number of cells at G2/M and greater activation of caspase-3.
- Nantes, Camilla I.,Pereira, Ingrid D.,Bai, Ruoli,Hamel, Ernest,Burnett, James C.,de Oliveira, Rodrigo J.,de F. C. Matos, Maria,Beatriz, Adilson,Yonekawa, Murilo K. A.,Perdomo, Renata T.,de Lima, Dênis P.,Bogo, Danielle,dos A. dos Santos, Edson
-
p. 449 - 458
(2020/01/25)
-
- Preparation method of diphenyl disulfide compounds
-
The invention discloses a preparation method of diphenyl disulfide compounds. The preparation method comprises the following steps: stirring an isopropyl magnesium halide Grignard reagent and a substituted halogen benzene compound in an organic solvent at -78 DEG C to -20 DEG C for 30-90 minutes to obtain a thoroughly halogen-magnesium exchanged substituted phenyl Grignard reagent; and adding dichlorodisulfide into the reaction system, slowly heating to room temperature after the reaction is finished, quenching the reaction by using a saturated ammonium chloride aqueous solution, extracting byusing ethyl acetate or diethyl ether, drying by using anhydrous magnesium sulfate, and concentrating the organic phase to obtain the diphenyl disulfide compounds. According to the method, the diphenyl disulfide compounds are prepared by taking the phenyl Grignard reagent as a raw material through a one-pot method, and has the following advantages: the synthetic route is short, the preparation process is simple, the cost is low, the operation is easy, the yield is excellent, and the industrial production is easy.
- -
-
Paragraph 0044; 0045; 0046; 0047; 0048; 0049; 0050
(2020/10/21)
-
- Regio- And Stereoselective Photoredox-Catalyzed Atom Transfer Radical Addition of Thiosulfonates to Aryl Alkynes
-
Despite extensive investigations, altering the regioselectivity of atom transfer radical addition (ATRA) to alkynes remains a highly desirable yet unachieved challenge. Guided by computational predictions, thiosulfonates were found herein as a tunable radical precursor for thiyl radicals instead of well-recognized sulfonyl radicals. Merging such a finding with ATRA to phenylacetylenes leads to a highly regio- and stereoselective approach to (E)-β-arylsulfonylvinyl sulfides. This protocol is feathered by mild conditions, low photocatalyst loading, no transition-metal catalyst required, and broad functional group compatibility. The successful application of our protocol in the late-stage functionalization of bioactive natural product derivatives demonstrates its synthetic utility. Mechanistic studies corroborate the photoredox-catalyzed ATRA pathway and reveal the pivotal role of thiyl radical, to which unprecedented regioselectivity was attributed.
- Peng, Zhiyuan,Yin, Haolin,Zhang, Hui,Jia, Tiezheng
-
supporting information
p. 5885 - 5889
(2020/08/12)
-
- TEMPO visible light photocatalysis: The selective aerobic oxidation of thiols to disulfides
-
TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) is well-established in orangocatalysis that usually work in synergy with transition-metal catalysis or semiconductor photocatalysis. Here, TEMPO was turned into a visible light photocatalyst to conduct the selective aerobic oxidation of thiols into disulfides. With O2 as an oxidant, a mild and efficient protocol for the selective oxidation of thiols into disulfides including symmetrical and unsymmetrical ones with 5 molpercent of TEPMO as a photocatalyst was developed at room temperature under the irradiation of 460 nm blue LEDs. It was found that a complex formed between TEMPO and thiols underpinned the visible light activity and disulfides were obtained in very high isolated yields. This work suggests that TEMPO takes diverse roles in for photocatalytic selective oxidative transformations with O2 as the oxidant.
- Xu, Hui,Zhang, Yu-Fei,Lang, Xianjun
-
supporting information
p. 1520 - 1524
(2019/12/09)
-
- Visible-light mediated facile dithiane deprotection under metal free conditions
-
Visible light mediated facile and selective dithiane deprotection under metal free conditions is developed. Eosin Y (1 mol%) proved to be an effective catalyst for the dithiane deprotection under the ambient photoredox conditions. The standard household compact fluorescent light source (CFL bulb) proved to be effective under open-air conditions in aqueous acetonitrile at room temperature. The protocol that exhibits a broad substrate scope and functional group tolerance has been shown to expand to a range of transformations for the electron-rich and -deficient thioacetals and thioketals. The synthetic utility of this protocol has also been demonstrated by gram-scale application.
- Dharpure, Pankaj D.,Bhowmick, Anindita,Warghude, Prakash K.,Bhat, Ramakrishna G.
-
-
- Direct Sulfenylation of the Purine C8-H Bond with Thiophenols
-
The one-step copper-mediated regioselective formation of the C8-S bond for purine derivatives with arylthiols was achieved using air as the green oxidant in the presence of 1.0 equiv of Na2CO3 and stoichiometric CuCl and 1,10-phenanthroline monohydrate. This method provides an economical, easy-to-handle, and effective method for the synthesis of 8-sulfenylpurine derivatives in moderate to excellent yields. The reaction is selective for C8 over C2 and C6. It also tolerates a free amine on the purine, and it has a wide substrate scope.
- Jiang, Wei,Zhuge, Juanping,Li, Jianxiao,Histand, Gary,Lin, Dongen
-
p. 2415 - 2425
(2020/02/04)
-
- Iodine/Manganese Catalyzed Sulfenylation of Indole via Dehydrogenative Oxidative Coupling in Anisole
-
This protocol describes an iodine/manganese catalytic system for dehydrogenative oxidative coupling reaction of indoles with thiols in anisole. Particularly, the dual roles of anisole have been first demonstrated as a solvent and as a promoter via the formation of an oxonium ion intermediate to accelerate the generation of products. A series of sulfenylindoles are readily constructed under aerobic mild reaction conditions. In addition, the achievement for preparing anticancer and anti-AIDS drugs testifies the practicability of this approach. The mechanism studies disclose probable alternative pathways and a single-electron transfer process are involved in this transformation. (Figure presented.).
- Li, Weihe,Wang, Hao,Liu, Shengping,Feng, Hua,Benassi, Enrico,Qian, Bo
-
supporting information
p. 2666 - 2671
(2020/05/25)
-
- Multicomponent Synthesis of Sulfones and Sulfides from Triarylbismuthines and Sodium Metabisulfite in Deep Eutectic Solvents
-
This study describes a novel and catalyst-free methodology for the multicomponent synthesis of a broad range of sulfones, disulfides, and sulfides from non-toxic triarylbismuthines (Ar3Bi) and sodium metabisulfite (Na2S2O5) in deep eutectic solvents (DESs). The fine tuning of the DESs properties allowed the solubility of all reagents, enhancing their reactivity, as well as, the recyclability of the reaction medium for at least 5 consecutive cycles. Thus, this versatile strategy uses non-toxic reagents without the need of metal catalysts in a sustainable solvent, being an interesting alternative to traditional hazardous protocols.
- Saavedra, Beatriz,Marset, Xavier,Guillena, Gabriela,Ramón, Diego J.
-
supporting information
p. 3462 - 3467
(2020/06/04)
-
- Thiol Activation toward Selective Thiolation of Aromatic C-H Bond
-
Direct C-S bond coupling is an attractive way to construct aryl sulfur ether, a building block for a variety of biological active molecules. Herein, we disclose an effective model for regioselective thiolation of the aromatic C-H bond by thiol activation instead of arene activation. Strikingly, this method has been applied into anisole derivatives that are not available in the arene activation approach to forge a single thioether isomer with high reactivity.
- Chen, Bin,Lei, Tao,Li, Xu-Bing,Nan, Xiao-Lei,Tung, Chen-Ho,Wang, Jing-Hao,Wu, Hao-Lin,Wu, Li-Zhu
-
supporting information
p. 3804 - 3809
(2020/06/04)
-
- Thiosulfonylation of Unactivated Alkenes with Visible-Light Organic Photocatalysis
-
A metal-free method for the vicinal thiosulfonylation of unactivated alkenes with thiosulfonates using 9-mesityl-10-methylacridinium perchlorate as the photo-organocatalyst with visible-light irradiation has been developed. The method can be performed in dimethyl carbonate under air at room temperature and features a broad functional group compatibility. Metrics indicate the green potential of the developed versus the state-of-the-art methodologies. Mechanistic studies revealed no single electron transfer but involvement of an energy transfer from the excited photo-organocatalyst to thiosulfonate reactant, subsequently providing a sulfenyl and a sulfonyl radical via homolytic cleavage.
- Abbaspour Tehrani, Kourosch,Ching, H. Y. Vincent,Gadde, Karthik,Guidetti, Andrea,Herrebout, Wouter A.,Maes, Bert U. W.,Mampuys, Pieter,Van Doorslaer, Sabine
-
p. 8765 - 8779
(2020/09/21)
-
- Extended Pummerer fragmentation mediated by carbon dioxide and cyanide
-
Pummerer rearrangement reactions generate sulfur (II) oxidation state from sulfur (IV) starting materials in the presence of activating reagents. We found unprecedented transformation of vinyl sulfoxide; disulfide formation reactions mediated by atmospheric pressure of carbon dioxide in extended Pummerer rearrangement reactions. Only under CO2 atmosphere, we observed moderate to high yields of disulfide starting from sulfur (IV) starting materials. Investigations on the reaction mechanism revealed that the degradation of the starting materials and the products was significant in the absence of CO2. Further evidence for the suggested reaction mechanism was obtained by a cross-over experiment and a radical trapping reagent.
- Liu, Jian,Kragh, Rasmus R.,Kamounah, Fadhil S.,Lee, Ji-Woong
-
-
- Method for synthesizing symmetric disulfide compound by taking aryl hydrazine and S8 as raw materials
-
The invention relates to a method for synthesizing a symmetric disulfide compound by taking aryl hydrazine and S8 as raw materials, and belongs to the technical field of organic synthesis; the methodis characterized in that the aryl hydrazine compound and S8 are used as substrates to react in a reaction solvent under the promotion of alkali to generate the symmetric disulfide organic compound, the reaction gas atmosphere is air or oxygen, the reaction temperature is 40 DEG C-100 DEG C, and the reaction time is 4-24 hours. The synthesis steps are simple, the reaction conditions are mild, S8 which is widely distributed in nature, low in price and easy to obtain is used as a sulfur source, S-S bonds can be constructed only under the promotion of alkali without transition metal catalysis, theyield is as high as 95%, the applicable reaction substrate range is wide, the operation is simple and feasible, the synthesis cost is low, the environmental pollution is small, and a new thought is provided for the synthesis of the symmetric disulfide organic compound.
- -
-
Paragraph 0045-0048
(2020/11/23)
-
- Mapping mechanisms in glycosylation reactions with donor reactivity: Avoiding generation of side products
-
The glycosylation reaction, which is key for the studies on glycoscience, is challenging due to its complexity and intrinsic side reactions. Thioglycoside is one of the most widely used glycosyl donors in the synthesis of complex oligosaccharides. However, one of the challenges is its side reactions, which lower its yield and limits its efficiency, thereby requiring considerable effort in the optimization process. Herein, we reported a multifaceted experimental approach that reveals the behaviors of side reactions, such as the intermolecular thioaglycon transformation and N-glycosyl succinimides, via the glycosyl intermediate. Our mechanistic proposal was supported by low temperature NMR studies that can further be mapped by utilizing relative reactivity values. Accordingly, we also presented our findings to suppress the generation of side products in solving this particular problem for achieving high-yield glycosylation reactions.
- Wang, Cheng-Chung,Chang, Chun-Wei,Lin, Mei-Huei,Wu, Chia-Hui,Chiang, Tsun-Yi
-
p. 15945 - 15963
(2021/01/18)
-