21784-96-3

The cross-electrophile coupling between unactivated alkyl bromides with arenesulfonyl cyanides catalyzed by Ni(acac)2under reductive conditions to form unsymmetrical sulfides is developed. This approach for sulfide synthesis is practical, relies on available, unfunctionalized materials such as alkyl (pseudo)halides, and is scalable. This catalytic strategy provides a complementary method for the preparation of unsymmetrical alkyl-aryl sulfides under mild conditions with good functional group tolerance.

An efficient reduction of sulfoxides to sulfides mediated by N-bromosuccinimide (NBS)/HCl system has been developed. This protocol shows good functional group compatibility as well as broad substrates scope with operational simplicity.

A cost effective and easily available CuI/DABCO catalytic system has been developed for the C–S cross-coupling reaction. This method is extremely useful for the thioetherification of aryl and heteroaryl halides, providing excellent yields and good chemoselectivity. We have also explored the mechanism of the reaction using DFT studies.

A palladium/copper-cocatalyzed Ullmann-type N-arylation of anilines using alkyl(aryl)sulfonium triflates as arylation reagents has been accomplished. The reaction enabled Caryl-S bond cleavage over Calkyl-S bond breakage of alkyl(aryl)sulfoniums by Pd(P(tBu)3)2/CuI and gave the corresponding N-arylated products in good to high yields. It was also significant that the reactions of aniline with asymmetric butyl(mesityl)(aryl)sulfonium triflates showed excellent selectivity, in which the aryl groups other than the bulky and electron-rich mesityl moieties were transformed.

The invention discloses a synthesis method of thioether compounds. The method comprises steps as follows: phosphorus trichloride and a solvent with uniformly distributed sulfoxide compounds are mixeduniformly, after mixing, the mixture is subjected to a reaction at the temperature of 20-25 DEG C for 0.5-6 h, and the thioether compounds are obtained, wherein the solvent is acetonitrile. Compared with the prior art, the synthesis method has the advantages that raw materials are cheap and easy to obtain, a reducer is cheap and easy to obtain and store, and a series of thioether compounds can beobtained.

An efficient route to deoxygenation of sulphoxides to sulphides with PCl3 under mild reaction condition was developed. PCl3 was used as a reducing agent for the first time to convert sulphoxides to sulphides. The mild conditions, use of cheap and readily available reagent, and broad substrate scope render it a useful strategy for preparing sulphides.

The C-S cross-coupling of aryl halides with alkyl thiols catalyzed by in-situ generated Ni (II) N-heterocyclic carbene (NHC) complexes is investigated. Good to excellent yields can be obtained for a variety of aryl halides when using 5 mol% of the Ni (II)-NHC catalyst and 1.5 eq. of KOtBu. Both the electronic and steric effects of the NHC ligands on the catalytic performance of Ni (II)-NHC, as well as the electronic effects of aryl halides on coupling reactivity are examined. The mechanism for Ni (II)-NHC catalyzed coupling reactions is also discussed.

The preparation of thioethers by S-alkylation of various thiols with alkyl halides under solvent-free reaction conditions using potassium fluoride on alumina (KF/Al2O3) as a solid catalyst has been investigated in detail with respect to three different modes of reaction activation (ultrasound irradiation, microwave irradiation, and conventional heating) for obtaining maximum yield of the thioether. The importance of KF/Al2O3 as a particularly efficient catalyst was corroborated for all three modes of reaction activation, although the reaction time was found to be strongly dependent on the mode of activation. The yield of the thioethers was also found to depend on the amount of the solid catalyst relative to the equimolar amounts of the two reactants.

A cost effective and easily available CuI/DABCO catalytic system has been developed for C-S cross-coupling reaction. This method is extremely useful for the thioetherification of aryl and heteroaryl halides providing excellent yields and good chemoselectivity.

In this article, we have presented a novel, efficient and environmentally benign method for one-pot, one-step and odorless synthesis of a wide range of unsymmetrical sulfides from the reaction of aryl/benzyl/alkyl halides with aryl boronic acids in the presence of S8, NaOH and a catalytic amount of CuI in PEG200 as green solvent at 40-60 °C. The products were obtained in moderate to excellent yields. More importantly, this reaction is applicable for the gram-scale preparation of the desired sulfides.

An efficient method for the deoxygenation of sulfoxides into their corresponding sulfides at room temperature using NaHSO3 in the presence of catalytic I2 has been reported.

A series of catalytic C - S coupling reactions utilizing well-defined Ni(II) PNP pincer complexes as precatalysts are reported (PNP = anion of 2,5-bis[(dialkyl/aryl-phosphino)methyl]pyrrole, abbreviated as P2RPyr). Coupling reactions employing a variety of aryl iodides and thiols in the presence of base and DMF proceed in good to excellent yield at 80°C with low catalyst loadings. Aryl bromides were found to result in substantially lower yields, and aryl chlorides were found to be unreactive under the catalytic conditions. In an effort to further understand the reactivity of the nickel PNP precatalysts, complexes of Ni(II) containing amide, alkoxide, hydroxide, thiolate, and hydrosulfide ligands have been prepared and examined in stoichiometric reactions relevant to carbon-heteroatom coupling. Full characterization of each nickel complex is provided, including solid-state structures. The results of stoichiometric reactions implicate a reduced Ni(I) species as the active catalyst, which forms by reduction of the Ni(II) precatalyst in the presence of excess thiolate. The facility in forming Ni(I) species is invoked to rationalize the observed activity among different Ni PNP precatalysts. (Chemical Equation Presented).

In this article, we have introduced catalytic application of copper ferrite nanoparticles (CuFe2O4) for one-pot odorless production of aryl alkyl thioethers using thiourea and alkyl bromides in wet polyethylene glycol as a green solvent. The catalyst was also successfully applied for one-pot synthesis of symmetrical diaryl trithiocarbonates via the reaction of sodium sulfide, carbon disulfide and aryl iodides under heterogeneous reaction condition. Magnetic copper ferrite nanoparticles were synthesized using iron (III) chloride and copper (II) chloride, and characterized using XRD, FT-IR, AAS, and TEM analysis. The catalyst was recycled using simple magnetic separation and reused for the five consecutive runs in the reaction of iodobenzene, thiourea and benzyl bromide without appreciable loss of activity.

A copper catalyzed one-pot protocol for the preparation of aryl alkyl thioethers and diaryl disulfides using carbon disulfide as the sulfur source and diethylamine in polyethylene glycol (PEG200) is described.

A series of carbonyl-phosphine oxide ligands were synthesized from 2-bromophenylaldehyde and used in Cu-catalyzed C-S coupling reactions. Aryl iodide and aryl bromide reacted with thiols efficiently upon catalysis under mild reaction conditions and a yiel

A series of carbonyl-phosphine oxide ligands were synthesized from 2-bromophenylaldehyde and used in Cu-catalyzed C-S coupling reactions. Aryl iodide and aryl bromide reacted with thiols efficiently upon catalysis under mild reaction conditions and a yiel

ortho-Alkynylbenzoic acid alkyl esters act as alkylating agents of thiol derivatives with PPh3AuCl in combination with AgOTf in 1,2-dichloroethane at 80 °C. The corresponding sulfide compounds are obtained in good to excellent yields.

Alkylation of cyclic secondary amines, thiols, and pyridazinones has been demonstrated with alkyl halides using Triton B as base and reaction medium.

The synthesis of bis-imino nickel(II) NNN pincer complexes of the type [NiCl2{C5H3N-2,6-(CHNArf) 2}]; Arf= C6H3-2,3-F2 (1), C6H3-2,5-F2 (2), C6H 3-3,4-F2 (3), C6H3-3,5-F2 (4), C6H2-2,3,4-F3 (5), C6H 2-2,3,6-F3 (6), C6H2-2,4,5-F 3 (7), C6H2-2,4,6-F3 (8), has been achieved and their reactivity in alkyl- and arylthiolation reactions of halobenzenes examined. The use of fluorinated substituents Arf on the imines has allowed the tuning of the electronics in these complexes and the influence of these substituents and those of the disulfides in the thiolation reactions have been analyzed.

A mild, palladium-free synthetic protocol for the cross-coupling reaction of vinyl or aryl iodides and thiols or selenols using, in certain embodiments, 10 mol % CuI and 10 mol % neocuproine, with NaOt-Bu as the base, in toluene at 110 ° C. A variety of vinyl/aryl sulfides and vinyl/aryl selenides can be synthesized in excellent yields from readily available iodides and thiols or selenols.

KF/Al2O3 efficiently catalyzes N-alkylation of heterocyclic, primary, and secondary amines and S-alkylation of thiols with a variety of alkyl halides. The N-alkylation and S-alkylation adducts were produced in good to excellent yields and in short times. Copyright Taylor & Francis Group, LLC.

Various aryl sulfides can be synthesized by nickel-catalyzed alkyl- or arylthiolation of aryl iodide with a disulfide compound. This reaction produces Ni(0) from NiBr2-bpy by the reduction with zinc, and this generated complex works as an activating species to convert ArI into ArSR under neutral conditions. Furthermore, this system enables the use of two RS groups in (RS)2.

Alkyl and aryl disulfides are reduced by zinc powder in the presence of AlCl3 in aqueous media to yield zinc thiolates. These thiolate anion species then react with alkyl tosylates to give sulfides in high to excellent yields.

Alkyl and aryl disulfides are reduced by zinc powder in the presence of AlCl3 in aqueous media to yield zinc thiolates. This thiolate anion species then react with alkyl tosylates to give sulfides in high execellent yields.

[reaction: see text] We report a mild, palladium-free synthetic protocol for the cross-coupling reaction of aryl iodides and thiols using 10 mol % CuI and 10 mol % neocuproine, with NaOt-Bu as the base, in toluene at 110 degrees C. Using this protocol, we have shown that a variety of aryl sulfides can be synthesized in excellent yields from readily available iodides and thiols.

An efficient procedure for preparation of various sulfides has been introduced through a simple reaction of disulfides with suitable alkyl or aryl halides which is promoted by commercial zinc powder in the presence of AlCl3 in aqueous media at 65°C.

The reaction between N-tosyldiarylsulfilimines and p-toluenethiolate anion did not take place in the dark even upon heating up to 62o but proceeded smoothly upon irradiation with visible light in DMF at room temperature, affording S-N bond cleavage products.

The nucleophilic attack of alkyl- and aryl-lithium compounds at the sulfenyl sulfur atom in thiosulfonic S-esters performs a convenient synthesis of aromatic sulfides which are obtained cleanly and in generally excellent yields.Considering that recently we have reported a ready preparation of thiosulfonic S-esters from sulfonyl chlorides, this sulfidation reaction completes an interesting general procedure for converting the laters to any symmetrical or unsymmetrical sulfides.

This paper desribes a new reaction for the conversion of sulfoxides to sulfides by boron trifluoride and sodium iodide, both readily available and low-cost reagents.Very short reaction times, easy work up and almost quantitative yields make this reaction interesting from a synthetic point of view.

The reactions of SnPh3 (n= 3 or 4) with mercury(II) chloride, bromine and iodine lead to phenyl-tin bond cleavage.In contrast, reactions with methyl iodide provide SnPh3 and MeSC6H4Me-p.Charge-transfer adducts are formed between SnPh3 (n= 1-4) and tetracyanoethylene or p-bromoanil.The values of λmax. of the complexes indicate similar donor character for SnPh3 (n= 2,3, or 4); however, the compound SnPh3(CH2SC6H4Me-p) is a stronger donor.

-