3463-02-3Relevant articles and documents
Production of Alkyl Aryl Sulfides from Aromatic Disulfides and Alkyl Carboxylates via a Disilathiane–Disulfide Interchange Reaction
Nakajima, Takumi,Takano, Ken,Maeda, Hiromu,Ogiwara, Yohei,Sakai, Norio
supporting information, p. 4103 - 4107 (2021/11/10)
The results of this study show that disilathiane is an effective mediator in the synthesis of alkyl aryl sulfides with disulfides and alkyl carboxylates. Mechanistic studies suggest that disilathiane promotes cleavage of the sulfur–sulfur bond of disulfides to generate thiosilane as a key intermediate. Diselenides were also applicable to this transformation to produce the corresponding selenides.
Site-Selective C?S Bond Formation at C?Br over C?OTf and C?Cl Enabled by an Air-Stable, Easily Recoverable, and Recyclable Palladium(I) Catalyst
Scattolin, Thomas,Senol, Erdem,Yin, Guoyin,Guo, Qianqian,Schoenebeck, Franziska
supporting information, p. 12425 - 12429 (2018/09/18)
This report widens the repertoire of emerging PdI catalysis to carbon–heteroatom, that is, C?S bond formation. While Pd0-catalyzed protocols may suffer from the formation of poisonous sulfide-bound off-cycle intermediates and lack of selectivity, the mechanistically diverse PdI catalysis concept circumvents these challenges and allows for C?S bond formation (S–aryl and S–alkyl) of a wide range of aryl halides. Site-selective thiolations of C?Br sites in the presence of C?Cl and C?OTf were achieved in a general and a priori predictable fashion. Computational, spectroscopic, X-ray, and reactivity data support dinuclear PdI catalysis to be operative. Contrary to air-sensitive Pd0, the active PdI species was easily recovered in the open atmosphere and subjected to multiple rounds of recycling.
The influence of electronic perturbations on the Sulfur-Fluorine Gauche Effect Dedicated to Prof. Dr. Antonio Togni on the occasion of his 60th birthday.
Thiehoff, Christian,Schifferer, Lukas,Daniliuc, Constantin G.,Santschi, Nico,Gilmour, Ryan
supporting information, p. 121 - 126 (2016/01/25)
Herein, a solution phase NMR conformer population analysis is employed to probe the effect of remote electronic perturbations on the conformational equilibria of a series of para-substituted β-fluorosulfides (1), sulfoxides (2) and sulfone derivatives (3). Conformations that allow for stabilizing stereoelectronic (σC-H → σ?C-F) and electrostatic (Fδ-...Sδ+) interactions predominate: this is consistent with the Sulfur-Fluorine Gauche Effect. The molar fractions (χ) of the two possible gauche conformers correlate linearly with the electron-withdrawing aptitude of the para-substituent, rendering the system ideally suited for a Hammett-type analysis. Despite the clear influence that the remote para-substituents have on conformer population, this is superseded by the oxidation state on sulfur (II, IV, VI), where an increased preference for the gauche conformer follows the trend: sulfide sulfone sulfoxide. It is envisaged that this proof of concept in controlling conformer population, either by proximal (oxidation state) or remote tuning (para-substituent), will find application in molecular design.
Alkylation of SH-heterocycles with diethyl phosphite using tetrachloroethylene as an efficient solvent
Quan, Zheng-Jun,Ren, Rong-Guo,Da, Yu-Xia,Zhang, Zhang,Wang, Xi-Cun
experimental part, p. 653 - 658 (2011/12/15)
Treatment of mercapto-heterocyclic compounds with diethyl phosphite in the presence of 4-dimethylaminopyridine (DMAP) in tetrachloroethylene has given the S-ethylated product in good yields and high chemoselectivity. This procedure is compatible with a wide range of SH-compounds such as 1,3,4-oxadiazole-2-thiol, 1,3,4-thiadiazole-2-thiol, benzo[d]thiazole-2-thiol, and substituted benzenethiol. Copyright
CONFORMATIONAL AND ELECTRONIC INTERACTION STUDIES OF α-SUBSTITUTED CARBONYL COMPOUNDS. VI. p-SUBSTITUTED α-PHENYLTHIOACETONES.
Olivato, Paulo R.,Guerrero, Sandra A.,Martins, Elizabeth A. L.
, p. 9 - 16 (2007/10/02)
The analysis of the νCO bands in the I.R. spectrum of p-substituted α-phenylthioacetones indicates a cis/gauche rotational isomerism.The slight solvent effect on the αc αg ratios on going from a non polar solvent to a polar one , for the title compounds, as well as the minute sensitivity of the νCO (cis) frequencies on going from electron-attracting to electron-donating substituents are interpreted on the grounds of the Field (F) and Inductive effects, which act in opposition in the cis rotamer, practically cancelling each other.The decreasing cis/gauche population ratio on going from electron-attracting to electron-donating substituents suggests the occurance of the hyperconjugative interaction in the gauche rotamers of the title compounds.The progressive shielding effect on the methylene and carbonyl carbon atoms in the 13C NMR spectra, on going from electron-donating to electron-attracting substituents is ascribed at least in part, to the "Reverse Polar Effect".Keywords: Conformational studies; electronic interaction; Reverse Polar Effect; I.R. spectroscopy; 13C NMR spectroscopy; p-substituted α-phenylthioacetones.
Reaction of Phenylnitrenium Ion with Sulphides. A Novel Synthetic Method for Aminophenyl Sulphide Derivatives
Takeuchi, Hiroshi,Hirayama, Shinji,Mitani, Michiharu,Koyama, Kikuhiko
, p. 521 - 528 (2007/10/02)
The reaction of phenyl azide with sulphides in the presence of both trifluoroacetic acid and trifluoromethanesulphonic acid to produce 2- and 4-aminophenyl sulphides (2) and (3) was investigated in order to obtain information on the following points: the kinetics of decomposition of phenyl azide, the effect of addition of benzene to reaction systems, the replacement of phenyl azide by 1-phenyl-2-methyl-4,6-diphenylpyridinium salt, and the steric and electronic effect of substituents in the sulphides.The products are formed through an azasulphonium ion by reaction of phenylnitrenium ion with sulphide, followed by rearrangement of the alkyl group in the azasulphonium ion.Sulphides with primary alykl groups larger than propyl result in selective formation of ortho-products (2), the mechanism of which is discussed in detail.
