Synthesis of Aryl Sulfides by Metal-Free Arylation of Thiols with Diaryliodonium Salts

Metal-free arylation of thiols with diaryliodonium salts has been developed. The application of a strong organic base ena-bles the C–S bond formation under mild and experimentally simple conditions. The method allows for the synthesis of aryl sulfides containing a broad range of aryl groups from an array of thiols, including aryl, heteroaryl, and alkyl ones. The mechanism of the reaction was studied by DFT calculations, demonstrating that is follows the inner sphere pathway involv-ing the incipient formation of Ar2I(SR) intermediate, followed by the reductive elimination.

Ni-Catalyzed Aryl Sulfide Synthesis through an Aryl Exchange Reaction

A Ni-catalyzed aryl sulfide synthesis through an aryl exchange reaction between aryl sulfides and a variety of aryl electrophiles was developed. By using 2-pyridyl sulfide as a sulfide donor, this reaction achieved the synthesis of aryl sulfides without using odorous and toxic thiols. The use of a Ni/dcypt catalyst capable of cleaving and forming aryl–S bonds was important for the aryl exchange reaction between 2-pyridyl sulfides and aryl electrophiles, which include aromatic esters, arenol derivatives, and aryl halides. Mechanistic studies revealed that Ni/dcypt can simultaneously undergo oxidative additions of aryl sulfides and aromatic esters, followed by ligand exchange between the generated aryl–Ni–SR and aryl–Ni–OAr species to furnish aryl exchanged compounds.

Ni-Catalyzed Aryl Sulfide Synthesis through an Aryl Exchange Reaction

A Ni-catalyzed aryl sulfide synthesis through an aryl exchange reaction between aryl sulfides and a variety of aryl electrophiles was developed. By using 2-pyridyl sulfide as a sulfide donor, this reaction achieved the synthesis of aryl sulfides without using odorous and toxic thiols. The use of a Ni/dcypt catalyst capable of cleaving and forming aryl–S bonds was important for the aryl exchange reaction between 2-pyridyl sulfides and aryl electrophiles, which include aromatic esters, arenol derivatives, and aryl halides. Mechanistic studies revealed that Ni/dcypt can simultaneously undergo oxidative additions of aryl sulfides and aromatic esters, followed by ligand exchange between the generated aryl–Ni–SR and aryl–Ni–OAr species to furnish aryl exchanged compounds.

Solvent-Mediated Switching Between Oxidative Addition and Addition-Oxidation: Access to β-Hydroxysulfides and β-Arylsulfones by Addition of Thiols to Olefins in the Presence of Oxone

The reaction between aryl olefins and thiols in the presence of Oxone in toluene-water (9:1, v/v) affords β-hydroxy-2-arylethyl aryl sulfides smoothly by interception of the intermediary thiyl radicals with aryl...

Improved, Odorless Access to Benzo[1,2-d;4,5-d′]- bis[1,3]dithioles and Tert-butyl Arylsulfides via C-S Cross Coupling

Benzo[1,2-d;4,5-d′]bis[1,3]dithioles are important building blocks within a range of functional materials such as fluorescent dyes, conjugated polymers, and stable trityl radicals. Access to these is usually gained via tert-butyl aryl sulfides, the synthesis of which requires the use of highly malodorous tert-butyl thiol and relies on SNAr-chemistry requiring harsh reaction conditions, while giving low yields. In the present work, S-tert-butyl isothiouronium bromide is successfully applied as an odorless surrogate for tert-butyl thiol. The C-S bond formation is carried out under palladium catalysis with the thiolate formed in situ resulting in high yields of tert-butyl aryl sulfides. The subsequent formation of benzo[1,2-d;4,5-d′]bis[1,3]dithioles is here achieved with scandium(III)triflate, a less harmful reagent than the usually used Lewis acids, e.g., boron trifluoride or tetrafluoroboric acid. This enables a convenient and environmentally more compliant access to high yields of benzo[1,2-d;4,5-d′]bis[1,3]dithioles.

Three-Dimensional Graphene Oxide-Supported Zinc Oxide Scaffold as a High-Efficiency Adsorbent for Desulfurization

Sulfur oxides are air pollutants derived mainly from the combustion of gasoline. Reducing the sulfur content of fluid catalytic cracking (FCC) gasoline is of key importance for the prevention and control of atmospheric pollution. We describe herein the fabrication and characterization of a porous, three-dimensional (3D) graphene oxide-supported zinc oxide (GO/ZnO) scaffold as an adsorbent for desulfurization with various model compounds and real FCC gasoline. The uniform and stable dispersion of ZnO nanoparticles on the surface of GO facilitates the specific binding of sulfides. Moreover, GO synergistically adsorbs aryl sulfides via [Formula: see text]–[Formula: see text] stacking interactions. The GO/ZnO nanosheets were further self-assembled into a 3D porous scaffold that effectively trapped sulfides and inhibited desorption. These scaffolds exhibited excellent desulfurization performance with maximum sulfur capacity up to 29.73[Formula: see text]mg S/g. This work provides a novel perspective on the fabrication of high-efficiency adsorbents for gasoline pretreatment.