- Synthesis of Aryl Methyl Sulfides from Arysulfonyl Chlorides with Dimethyl Carbonate as the Solvent and C1 Source
-
A new procedure for the synthesis of aryl methyl sulfides from dimethyl carbonate (DMC) and arylsulfonyl chlorides has been achieved. In this strategy, DMC plays a dual role as both, C1 building block and green solvent. Arylsulfonyl chlorides served as the sulfur precursors, and a variety of aryl methyl sulfides were obtained in moderate to excellent yields with good functional group tolerance. Additionally, alkylsulfonyl chloride and dibenzyl carbonate are proven to be suitable substrates as well.
- Miao, Ren-Guan,Qi, Xinxin,Wu, Xiao-Feng
-
supporting information
p. 5219 - 5221
(2021/10/19)
-
- Copper-Catalyzed Methylthiolation of Aryl Iodides and Bromides with Dimethyl Disulfide in Water
-
An efficient route to aryl methyl sulfides through the copper-catalyzed coupling reaction of aryl iodides or bromides with dimethyl disulfide in water is described. Electron-donating and electron-withdrawing functional groups in the substrates were tolerated, and the corresponding products were obtained in moderate to good yields.
- Wang, Ying-Yu,Wu, Xiang-Mei,Yang, Ming-Hua
-
supporting information
(2020/07/20)
-
- A visible-light photocatalytic thiolation of aryl, heteroaryl and vinyl iodides
-
The general catalytic synthesis of aryl and vinyl thioethers from readily available halides remains a challenge. Herein we report a unified method for the thiolation of aryl and vinyl iodides with dialkyl disulfides using visible light photoredox catalysis. A range of thioether products bearing diverse functional groups can be accessed in high yield and with excellent chemoselectivity. We demonstrate the versatility of this method through the expedient synthesis of a family of thioether-rich natural products. A detailed investigation of the photocatalytic mechanism is presented from both steady-state and time-resolved luminescent quenching as well as transient absorption spectroscopy experiments.
- Czyz,Weragoda,Monaghan,Connell,Brzozowski,Scully,Burton,Lupton,Polyzos
-
supporting information
p. 1543 - 1551
(2018/03/08)
-
- Enantioselective copper catalysed intramolecular C-H insertion reactions of α-diazo-β-keto sulfones, α-diazo-β-keto phosphine oxides and 2-diazo-1,3-diketones; the influence of the carbene substituent
-
Enantioselectivities in C-H insertion reactions, employing the copper-bis(oxazoline)-NaBARF catalyst system, leading to cyclopentanones are highest with sulfonyl substituents on the carbene carbon, and furthermore, the impact is enhanced by increased steric demand on the sulfonyl substituent (up to 91%ee). Enantioselective intramolecular C-H insertion reactions of α-diazo-β-keto phosphine oxides and 2-diazo-1,3-diketones are reported for the first time.
- Shiely, Amy E.,Slattery, Catherine N.,Ford, Alan,Eccles, Kevin S.,Lawrence, Simon E.,Maguire, Anita R.
-
supporting information
p. 2609 - 2628
(2017/04/01)
-
- Electrophilic alkylation of pseudotetrahedral nickel(II) arylthiolate complexes
-
A kinetic study is reported for reactions of pseudotetrahedral nickel(II) arylthiolate complexes [(TpR,Me)Ni-SAr] (TpR,Me = hydrotris{3-R-5-methyl-1-pyrazolyl}borate, R = Me, Ph, and Ar = C6H5, C6H4-4-Cl, C6H4-4-Me, C6H4-4-OMe, 2,4,6-Me3C6H2, 2,4,6-iPr3C6H2) with organic electrophiles R'X (i.e., MeI, EtI, BzBr) in low-polarity organic solvents (toluene, THF, chloroform, dichloromethane, or 1,2-dichloroethane), yielding a pseudotetrahedral halide complex [(TpR,Me)Ni-X] (X = Cl, Br, I) and the corresponding organosulfide R'SAr. Competitive reactions with halogenated solvents and adventitious air were also examined. Akin to reactions of analogous and biomimetic zinc complexes, a pertinent mechanistic question is the nature of the reactive nucleophile, either an intact thiolate complex or a free arylthiolate resulting from a dissociative pre-equilibrium. The observed kinetics conformed to a second-order rate law, first order with respect to the complex and electrophile, and no intermediate complexes were observed. In the absence of a mechanistically diagnostic rate law, a variety of mechanistic probes were examined, including kinetic effects of varying the metal, solvent, electrophile, and temperature, as well as the 3-pyrazolyl and arylthiolate substituents. Compared to zinc analogues, the effect of Ni-SAr covalency is also of interest herein. The results are broadly interpreted with respect to the disparate mechanistic pathways.
- Deb, Tapash,Jensen, Michael P.
-
supporting information
p. 87 - 96
(2015/03/03)
-
- Sequential deracemization of sulfoxides via whole-cell resolution and heterogeneous oxidation
-
A new concept for the synthesis of asymmetric sulfoxides exploiting sequential deracemization of racemic (rac) sulfoxides using a two-stage protocol had been developed. Enantio-pure sulfoxide was obtained using Escherichia coli (E. coli) cells to catalyze the reduction of (R)-sulfoxide to the thioether, and then using a heterogeneous Ta2O5-SiO2 catalyst for catalyzing the oxidation of the ethers to the rac-sulfoxide. The performance of E. coli depended on the strain and the conditions under which the bacteria growth was carried out (e.g. source of carbon, presence of vitamins, and concentration of dimethyl sulfoxide, DMSO). Under optimized conditions, the E. coli cells performed the rac-sulfoxide resolution for different sufoxides leading to the best enantiomeric excess (ee) of around 62% (S)-MTSO (methyl tolyl sulfoxide) with 49% conversion of the rac-MTSO. The sequential deracemization process applied for rac-MTSO was cyclically performed leading to 97.5% ee of (S)-sulfoxide and a 56% yield in (S)-sulfoxide after three deracemization cycles of rac-MTSO.
- Tudorache, Madalina,Nica, Simona,Bartha, Emerich,Lupan, Iulia,Parvulescu, Vasile I.
-
-
- The cathodic cleavage of the S-P bond. Synthesis and electrochemical behaviour of sulfonamide phosphorus analogues
-
P-diphenylarylsulfophosphamides can be obtained by condensation of Ph2PLi on various arylsulfonyl chlorides. These sulfonamide phosphorus analogues exhibit facile cathodic cleavage reaction yielding, after quenching, diphenylphosphinic acid and arylsulfide.
- Pilard, Jean-Francois,Simonet, Jacques
-
p. 3735 - 3738
(2007/10/03)
-
- An Efficient Synthesis of Unsymmetrical Sulfides from Organic Disulfides and Aromatic Compounds
-
In the presence of an active acidic catalyst generated from SbCl5 and AgSbF6, the sulfenylation reaction of aromatic compounds with organic disulfides smoothly proceeds in refluxing 1,2-dichloroethane to afford the corresponding unsymmetrical sulfides in high yields.
- Mukaiyama, Teruaki,Suzuki, Kaoru
-
-