- Photocatalytic synthesis method of aryl thioether and derivatives thereof
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The invention belongs to the field of organic synthesis, and particularly relates to a photocatalytic synthesis method of aryl thioether and derivatives thereof. The synthesis method comprises the steps: dissolving an N-(sulfanyl) amide compound into a methyl aromatic compound under the protection of inert gas, and thus obtaining the aryl thioether compound under the action of light, a catalyst, aligand and alkali. According to the method, the coupling reaction of a C-S bond is completed through visible light induction by utilizing a light/Ni dual-catalytic system, so that the method has goodfunctional group compatibility, and the C-S bond compound can be selectively and efficiently constructed in one step. The method has the advantages of simple catalytic system, mild reaction conditions, economical, simple and easily available substrate, simple reaction operation and the like.
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Paragraph 0096; 0097; 0098; 0099
(2021/04/03)
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- Transition-metal-free decarboxylative thiolation of stable aliphatic carboxylates
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A transition-metal-free decarboxylative thiolation protocol is reported in which primary, secondary, tertiary (hetero)aryl acetates and α-CN substituted acetates undergo the decarboxylative thiolation smoothly, to deliver a variety of functionalized aryl alkyl sulfides in moderate to excellent yields. Aryl diselenides are also amenable substrates for construction of C-Se bonds under the simple and mild reaction conditions. Moreover, the protocol is successfully applied to the late-stage modification of pharmaceutical carboxylates with satisfactory chemoselectivity and functional-group compatibility. This journal is
- Xing, Wei-Long,Liu, De-Guang,Fu, Ming-Chen
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p. 4593 - 4597
(2021/02/03)
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- Transition metal-free coupling reactions of benzylic trimethylammonium salts with di(hetero)aryl disulfides and diselenides
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A new protocol was developed to synthesize (enantioenriched) thioethers and selenoethers from (chiral) benzylic trimethylammonium salts and di(hetero)aryl disulfides or diselenides. These syntheses were promoted by the presence of weak base and did not require the use of any transition metal, and resulted in the target products with good to excellent yields (72-94%). Using quaternary ammonium salts synthesized from enantiomerically enriched amines led to highly enantiopure benzylic thioethers and selenoethers (94-99% ee) with configurations reversed from those of their enantioenriched quaternary ammonium salts. This journal is
- Li, Fuhai,Wang, Dan,Chen, Hongyi,He, Ze,Zhou, Lihong,Zeng, Qingle
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supporting information
p. 13029 - 13032
(2020/11/07)
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- Nanolayered cobalt-molybdenum sulphides (Co-Mo-S) catalyse borrowing hydrogen C-S bond formation reactions of thiols or H2S with alcohols
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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.
- Corma, Avelino,Sorribes, Iván
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p. 3130 - 3142
(2019/03/13)
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- Alkyl Sulfides as Promising Sulfur Sources: Metal-Free Synthesis of Aryl Alkyl Sulfides and Dialkyl Sulfides by Transalkylation of Simple Sulfides with Alkyl Halides
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A site-selective metal-free dealkylative approach to synthesize aryl alkyl and symmetrical dialkyl sulfides has been developed. This procedure is convenient and has wide functional group tolerance giving rise to sulfides carrying various alkyl chains from simple alkyl sulfides and alkyl halides in good to excellent yields. This transalkylation proceeds by an ionic mechanism via sulfonium intermediates and it was proposed that dimethylacetamide (DMAC) may participate in part to promote the reaction.
- Liu, Ting,Qiu, Renhua,Zhu, Longzhi,Yin, Shuang-Feng,Au, Chak-Tong,Kambe, Nobuaki
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supporting information
p. 3833 - 3837
(2018/12/05)
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- Regioselective Synthesis of Selenide Ethers through a Decarboxylative Coupling Reaction
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An efficient and selective approach to the synthesis of selenide ethers containing one or two geminal C–Se bonds from readily available diselenides and phenylacetic acids was developed. Compounds containing one C–Se bond were prepared by employing air as the oxidant under metal-free conditions, whereas compounds having two geminal C–Se bonds were formed via the iron(III) chloride/oxygen/cesium carbonate (FeCl3/O2/Cs2CO3) system. Moreover, 1,2-diphenyldisulfane also could be smoothly converted into the corresponding sulfur ether product under the standard reaction conditions. (Figure presented.).
- Cui, Fei-Hu,Chen, Jing,Su, Shi-Xia,Xu, Yan-Li,Wang, Heng-Shan,Pan, Ying-Ming
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p. 3950 - 3961
(2017/11/20)
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- Synthesis of thioethers by ini3-catalyzed substitution of siloxy group using thiosilanes
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The substitution of a siloxy group using thiosilanes smoothly occurred in the presence of InI3 catalyst to yield the corresponding thioethers. InI3was a specifically effective catalyst in this reaction system, while other typical Lew
- Nishimoto, Yoshihiro,Okita, Aya,Baba, Akio,Yasuda, Makoto
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- A comparative study of Cu(II)-assisted vs Cu(II)-free chalcogenation on benzyl and 2°/3°-cycloalkyl moieties
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A relative synthetic strategy toward intermolecular oxidative C -Chalcogen bond formation of alkanes has been illustrated using both Cu(II) assisted vs Cu(II) free conditions. This led to construction of a comparative study of hydrocarbon benzylic and 2°/ 3°-cycloalkyl moieties bond sulfenylation and selenation protocol by the chalcogen sources, particularly sulfur and selenium, respectively. In addition, this protocol disclosed the auspicious formation of sp3 C-S coupling products over leading the sp3 C-N coupling products by using 2-mercaptobenzothiazole (MBT) substrates.
- Sahoo, Santosh K
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p. 2151 - 2157
(2016/01/12)
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- Photosensitized oxidation of aryl benzyl sulfoxides. Evidence for nucleophilic assistance to the c-s bond cleavage of aryl benzyl sulfoxide radical cations
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The radical cations of a series of aryl benzyl sulfoxides (4-X-C6H4CH2SOC6H4Y+?) have been generated by photochemical oxidation of the parent sulfoxides sensitized by 3-cyano-N-methylquinolinium perchlorate (3-CN-NMQ+ClO4-). Steady-state photolysis experiments showed the prevailing formation of benzylic products deriving from the C-S fragmentation in the radical cations, together with sulfur-containing products. Formation of sulfoxide radical cations was unequivocally established by laser flash photolysis experiments showing the absorption bands of 3-CN-NMQ? (λmax = 390 nm) and of the radical cations (λmax = 500-620 nm). The decay rate constants of radical cations, determined by LFP experiments, decrease by increasing the electron-donating power of the arylsulfinyl Y substituent and to a smaller extent by increasing the electron-withdrawing power of the benzylic X substituent. A solvent nucleophilic assistance to the C-S bond cleavage has been suggested, supported by the comparison of substituent effects on the same process occurring in aryl tert-butyl sulfoxide radical cations. DFT calculations, performed to determine the bond dissociation free energy in the radical cations, the transition state energies associated with the unimolecular C-S bond cleavage, and the charge and spin delocalized on their structures, were also useful to endorse the nucleophilic assistance to the C-S scission.
- Del Giacco, Tiziana,Lanzalunga, Osvaldo,Lapi, Andrea,Mazzonna, Marco,Mencarelli, Paolo
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p. 2310 - 2318
(2015/09/08)
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- Iodine-mediated thioetherification of alcohols with disulfides or NaSh under microwave irradiation
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An efficient and novel method for the thioetherification of an alcohol with disulfides or NaSH under microwave irradiation is presented. In the presence of iodine, a variety of alcohols were smoothly S-alkylated with disulfides or NaSH to give the corresponding thioethers in moderate to excellent yields. Copyright
- Hu, Bolun,Sun, Leilei,Tang, Riyuan,Hu, Huanan
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p. 2556 - 2562,7
(2020/09/16)
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- Synthesis of a wide range of thioethers by indium triiodide catalyzed direct coupling between alkyl acetates and thiosilanes
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An indium triiodide-catalyzed substitution of the acetoxy group in alkyl acetates with thiosilanes provides access to a variety of thioethers. The method is efficient for a wide scope of acetates such as primary alkyl, secondary alkyl, tertiary alkyl, allylic, benzylic, and propargylic acetates.
- Nishimoto, Yoshihiro,Okita, Aya,Yasuda, Makoto,Baba, Akio
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supporting information; experimental part
p. 1846 - 1849
(2012/06/18)
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- TAPC-catalyzed synthesis of thioethers from thiols and alcohols
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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.
- Bahrami, Kiumars,Khodaei, Mohammad Mehdi,Khodadoustan, Nayere
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experimental part
p. 2206 - 2210
(2011/10/09)
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- One-pot reductive sulfenylation and thiocyanation of carbonyl compounds in ionic liquid media
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The first example of an efficient one-pot reductive sulfenylation and thiocyanation of carbonyl compounds in environmentally benign ionic liquid (IL) media is reported. The process involves reduction of carbonyl compounds with NaBH4 in the IL [bmim]BF4 followed by I2-catalyzed reaction of the resulting alcohols with aromatic/aliphatic thiols or ammonium thiocyanate in the same vessel to afford sulfides or thiocyanates, respectively, in excellent yields (78-93%). Notably, the protocol precludes the necessity to prepare and isolate the intermediate alcohols in a separate step as they are formed in situ, and the IL used can be recycled easily for further use without any loss of efficiency. Copyright
- Yadav, Lal Dhar S.,Garima,Kapoor, Ritu
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experimental part
p. 100 - 112
(2011/03/17)
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- Bimetallic system for the synthesis of diorganyl selenides and sulfides, chiral β-seleno amines, and seleno- and thioesters
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The bimetallic reagent Sn(II)/Cu(II) in [bmim]BF4 was efficiently used for the cleavage of diaryl diselenides and disulfides and reacts with a variety of organic substrates, such as organic halides, acid chlorides, and β-amino mesylates affording the diorganyl selenides and sulfides within very short reaction times, under mild conditions and with excellent yields, using BMIM-BF4 as a reusable solvent.
- Gul, Kashif,Narayanaperumal, Senthil,Dornelles, Luciano,Rodrigues, Oscar E.D.,Braga, Antonio Luiz
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supporting information; experimental part
p. 3592 - 3596
(2011/07/31)
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- Silica nanoparticles as a reusable catalyst: A straightforward route for the synthesis of thioethers, thioesters, vinyl thioethers and thio-Michael adducts under neutral reaction conditions
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A simple and straightforward route for the synthesis of thioethers, thioesters, vinyl thioethers and thio-Michael adducts has been demonstrated using silica nanoparticles (NPs) as a reusable catalyst via the 1,2-addition of thiols to alkenes, alkynes and alkyl/acyl halides, and the 1,4-addition of thiols to conjugated alkenes at room temperature.
- Banerjee, Subhash,Das, Jayanta,Alvarez, Richard P.,Santra, Swadeshmukul
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experimental part
p. 302 - 306
(2010/06/13)
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- Unusual cleavage of ethers by thiophenol on the surface of silica gel impregnated with indium(III) chloride under microwave irradiation: Efficient procedure for the synthesis of thioethers through transthioetherification
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Cyclic and open-chain benzylic ethers undergo cleavage by thiophenol on the surface of silica gel impregnated with indium(III) chloride under microwave irradiation to produce the corresponding di- and monothioethers.
- Ranu, Brindaban C.,Samanta, Sampak,Hajra, Alakananda
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p. 987 - 989
(2007/10/03)
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- Co-C bond cleavage in the reactions of alkyl, benzyl and heteroaromaticmethyl cobaloximes with arene sulfenyl chloride: Homolytic and heterolytic pathways
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The reactions of arene sulfenyl chlorides, ArSCl, (Ar=Ph, C6Cl5, 2,4 (NO2)2C6H3) with organocobaloximes, RCo(dmgH)2Py, (R=alkyl, benzyl and heteroaromaticmethyl) were carried out under thermal and photochemical conditions. A variety of organic and organometallic products are formed depending upon the substrate cobaloxime. For 3-methoxybenzyl and heteroaromaticmethyl cobaloximes the results suggest that they represent a unique class of cobaloximes whereby both the aromatic ring as well as the Co-C bond are highly activated towards attack by the arene sulfenyl chloride. Both homolytic as well as heterolytic pathways are operative.
- Gupta,Dixit, Vandana,Das, Indira
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- DIRECT CONVERSION OF CARBOXYLIC ACIDS AND CARBOXYLIC ESTERS INTO S,S'-DIPHENYL ACETALS AND PHENYL SULFIDES WITH THEXYLPHENYLTHIOBORANE
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Reaction of carboxylic acids with thexylphenylthioborane in methylene chloride at room temperature gives S,S-diphenyl acetals in high yields and carboxylic esters are converted into phenyl sulfides in the presence of zinc iodide under similar conditions.
- Kim, Sunggak,Kim, Sung Soo
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p. 1913 - 1916
(2007/10/02)
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- The Mechanism of the Reaction of (Arylthio)trimethylgermanes with Benzyl Bromides Giving Aryl Benzyl Sulfides. A Kinetic Study
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A kinetic study has been conducted on the reaction of (arylthio)trimethylgermanes with benzyl bromides.The reaction was found to be second order and the rate was largely accelerated in polar solvents.Both ρ values due to substituents on arylthio and benzyl groups revealed nucleophilic attack of the sulfur atom on benzylic carbon atom as the reaction mechanism.Rates of the reactions of trimethyl(p-tolylthio)stannane with substituted benzyl chlorides were also examined to compare the substituent effects.Steric crowd around the sulfur atom has been found as an important factor to control the reaction mechanism.
- Kozuka, Seizi,Tamura, Shoji,Ishibashi, Satoshi,Ohya, Sadamu,Tagaki, Waichiro
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p. 4061 - 4066
(2007/10/02)
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- Isotope effects in nucleophilic substitution reactions. IV. The effect of changing a substituent at the α carbon on the structure os SN2 transition states
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Kinetic studies, secondary α-deuterium kinetic isotope effects, primary chlorine kinetic isotope effects (1), Hammett ρ values determined by changing the substituent in the nucleophile, and activation parameters have been used to determine the detailed (relative) structures of the transition states for the S2 reactions between para-substituted benzyl chlorides and thiophenoxide ion.A rationale for the U-shaped Hammett ρ plots observed when para-substituted benzyl compounds react with negatively charged nucleophiles is also presented.
- Westaway, Kenneth Charles,Waszczylo, Zbigniew
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p. 2500 - 2520
(2007/10/02)
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