15570-03-3

Upstream product

• 108-98-5 thiophenol 
• 3278-38-4 S-phenyl O-ethylxanthate 
• 500582-62-7 ClC₆H₄CH₂N⁽²⁾H₂ 
• 500582-61-6 CH₃OC₆H₄CH₂N⁽²⁾H₂ 
• 930-69-8 sodium thiophenolate 

Downstream Products

• 777-80-0 methyl 3-(phenylthio)isobutyrate 
• 98585-81-0 Bicyclo<1.1.1>pent-1-ylphenylthioether 
• 52190-44-0 2-(Phenylthio)hexanal 
• 1393672-48-4 (E)-(3-deutero-3-hexylnon-1-en-1-yl)(phenyl)sulfane 
• 1383467-81-9 C₁₅H₁₂⁽²⁾H₂OS 
• 1383467-82-0 C₁₅H₁₃⁽²⁾HOS 
• 1383467-83-1 C₁₅H₁₃⁽²⁾HOS 
• 1333249-00-5 C₂₀H₂₅⁽²⁾HS₂ 
• 1333249-01-6 C₂₀H₂₄⁽²⁾H₂S₂ 

Relevant academic research and scientific papers

Nitric oxide reactivity of [2Fe-2S] clusters leading to H2S generation

The crosstalk between two biologically important signaling molecules, nitric oxide (NO) and hydrogen sulfide (H2S), proceeds via elusive mechanism(s). Herein we report the formation of H2S by the action of NO on synthetic [2Fe-2S] clusters when the reaction environment is capable of providing a formal H? (e-/H+). Nitrosylation of (NEt4)2[Fe2S 2(SPh)4] (1) in the presence of PhSH or tBu3PhOH results in the formation of (NEt 4)[Fe(NO)2(SPh)2] (2) and H2S with the concomitant generation of PhSSPh or tBu3PhO ?. The amount of H2S generated is dependent on the electronic environment of the [2Fe-2S] cluster as well as the type of H ? donor. Employment of clusters with electron-donating groups or H? donors from thiols leads to a larger amount of H 2S evolution. The 1/NO reaction in the presence of PhSH exhibits biphasic decay kinetics with no deuterium kinetic isotope effect upon PhSD substitution. However, the rates of decay increase significantly with the use of 4-MeO-PhSH or 4-Me-PhSH in place of PhSH. These results provide the first chemical evidence to suggest that [Fe-S] clusters are likely to be a site for the crosstalk between NO and H2S in biology.

Enantioselective Hydrothiolation: Diverging Cyclopropenes through Ligand Control

In this article, we advance Rh-catalyzed hydrothiolation through the divergent reactivity of cyclopropenes. Cyclopropenes undergo hydrothiolation to provide cyclopropyl sulfides or allylic sulfides. The choice of bisphosphine ligand dictates whether the pathway involves ring-retention or ring-opening. Mechanistic studies reveal the origin for this switchable selectivity. Our results suggest the two pathways share a common cyclopropyl-Rh(III) intermediate. Electron-rich Josiphos ligands promote direct reductive elimination from this intermediate to afford cyclopropyl sulfides in high enantio- A nd diastereoselectivities. Alternatively, atropisomeric ligands (such as DTBM-BINAP) enable ring-opening from the cyclopropyl-Rh(III) intermediate to generate allylic sulfides with high enantio- A nd regiocontrol.

The Effect of Viscosity on the Diffusion and Termination Reaction of Organic Radical Pairs

The effect of viscosity on the diffusion efficiency (Fdif) of an organic radical pair in a solvent cage and the termination mechanism, that is, the selectivity of disproportionation (Disp) and combination (Comb) of the geminated caged radical pair and the diffused radicals encountered, were investigated quantitatively by following the photolysis of dimethyl 2,2′-azobis(2-methylpropionate) (V-601) in the absence and presence of PhSD. Fdif and Disp/Comb selectivity outside the cage [Disp(dif)/Comb(dif)] are highly sensitive to the viscosity. In contrast, the Disp/Comb selectivity inside the cage [Disp(cage)/Comb(cage)] is rather insensitive. The difference in viscosity dependence between Disp(cage)/Comb(cage) and Disp(dif)/Comb(dif) is explained by the spin state of the radical pair inside and outside the cage and the spin state dependent configurational changes of the radical pair upon their collision. Given that the configurational change of the radicals associates the displacement and reorganization of solvents around the radicals, the termination outside the cage, which requires larger change than that inside the cage, is highly viscosity dependent. Furthermore, while the bulk viscosity of each solvent shows good correlation with Fdif and Disp/Comb selectivity, microviscosity is the better parameter predicting Fdif and Disp(dif)/Comb(dif) selectivity regardless of the solvents.

Visible-Light Photocatalytic Synthesis of Amines from Imines via Transfer Hydrogenation Using Quantum Dots as Catalysts

CdSe/CdS core/shell quantum dots (QDs) can be used as stable and highly active photoredox catalysts for efficient transfer hydrogenation of imines to amines with thiophenol as a hydrogen atom donor. This reaction proceeds via a proton-coupled electron transfer (PCET) from the QDs conduction band to the protonated imine followed by hydrogen atom transfer from the thiophenol to the α-aminoalkyl radical. This precious metal free transformation is easy to scale up and can be carried out by a one-pot protocol directly from aldehyde, amine, and thiophenol. Additional advantageous features of this protocol include a wide substrate scope, high yield of the amine products, extremely low catalyst loading (0.001 mol %), high turnover number (105), and the mild reaction conditions of using visible light or sun light at room temperature in neutral media.

Alkyl and Aryl Thiol Addition to [1.1.1]Propellane: Scope and Limitations of a Fast Conjugation Reaction

Herein the addition of different thiols to the strained carbon–carbon bond of [1.1.1]propellane (1) is reported. The reaction pathway was investigated, addition reactions with substituted thiols, hydrogen sulfide and protected cysteine were performed, and

Atom-efficient gold(I)-chloride-catalyzed synthesis of α-sulfenylated carbonyl compounds from propargylic alcohols and aryl thiols: Substrate scope and experimental and theoretical mechanistic investigation

Gold(I)-chloride-catalyzed synthesis of α-sulfenylated carbonyl compounds from propargylic alcohols and aryl thiols showed a wide substrate scope with respect to both propargylic alcohols and aryl thiols. Primary and secondary aromatic propargylic alcohol

A gold(I)-catalyzed route to α-sulfenylated carbonyl compounds from propargylic alcohols and aryl thiols

A one-step atom efficient gold(i)-catalyzed route to α-sulfenylated ketones and aldehydes from propargylic alcohols and aryl thiols is described.

Kinetics and mechanism of the aminolysis of S-aryl O-ethyl dithiocarbonates in acetonitrile

The aminolysis of S-aryl O-ethyl dithiocarbonates with benzylamines are studied in acetonitrile at -25.0°C. The βX (βnuc) values are in the range 0.67-0.77 with a negative cross-interaction constant, ρXZ = -0.24, which are interpreted to indicate a concerted mechanism. The kinetic isotope effects involving deuterated benzylamine nucleophiles (XC6H4CH 2ND2) are large, kH/kD = 1.41-1.97, suggesting that the N-H(D) bond is partially broken in the transition state by forming a hydrogen-bonded four-center cyclic structure. The concerted mechanism is enforced by the strong push provided by the EtO group which enhances the nucleofugalities of both benzylamine and arenethiolate from the putative zwitterionic tetrahedral intermediate.

Ion-neutral complex formation and hydrogen-shifts in the alkene loss from ionized alkyl phenyl thioethers in the gas phase

The mechanistic aspects of alkene loss from ionized ethyl- and n-propyl phenyl thioethers have been studied by use of deuterium labelling and tandem mass spectrometry. Loss of ethene from the molecule ion of ethyl phenyl thioether proceeds predominantly b