891-70-3

Upstream product

• 401-78-5 3-bromo-1-trifluoromethylbenzene 
• 1449-46-3 benzyltriphenylphosphonium bromide 
• 68-12-2 N,N-dimethyl-formamide 
• 100-42-5 styrene 
• 51907-90-5 <(3-Trifluormethyl)phenyl>phosphonsaeure 
• 454-89-7 3-Trifluoromethylbenzaldehyde 
• 1080-32-6 O,O-diethyl benzylphosphonate 
• 401-81-0 m-trifluoromethylphenyl iodide 
• 536-74-3 phenylacetylene 
• 140-10-3 (E)-3-phenylacrylic acid 
• 1179807-07-8 1-(3-trifluoromethylphenyl)azopyrrolidine 
• 98-08-8 α,α,α-trifluorotoluene 
• 1423-26-3 (meta-(trifluoromethyl)phenyl)boronic acid 
• 98-46-4 3-trifluoromethylnitrobenzene 

Relevant academic research and scientific papers

Non-Chelate-Assisted Palladium-Catalyzed Aerobic Oxidative Heck Reaction of Fluorobenzenes and Other Arenes: When Does the C?H Activation Need Help?

The pyridone fragment in the ligand [2, 2’-bipyridin]-6(1H)-one (bipy-6-OH) enables the oxidative Heck reaction of simple arenes with oxygen as the sole oxidant and no redox mediator. Arenes with either electron-donating or electron-withdrawing groups can be functionalized in this way. Experimental data on the reaction with toluene as the model arene shows that the C?H activation step is turnover limiting and that the ligand structure is crucial to facilitate the reaction, which supports the involvement of the pyridone fragment in the C?H activation step. In the case of fluoroarenes, the alkenylation of mono and 1,2-difluoro benzenes requires the presence of bipy-6-OH. In contrast, this ligand is detrimental for the alkenylation of 1,3-difluoro, tri, tetra and pentafluoro benzenes which can be carried out using just [Pd(OAc)2]. This correlates with the acidity of the fluoroarenes, the most acidic undergoing easier C?H activation so other steps of the reaction such as the coordination-insertion of the olefin become kinetically important for polyfluorinated arenes. The use of just a catalytic amount of sodium molybdate as a base proved to be optimal in all these reactions. (Figure presented.).

Pd-Catalyzed Cross-Coupling of Organostibines with Styrenes to Give Unsymmetric (E)-Stilbenes and (1 E,3 E)-1,4-Diarylbuta-1,3-dienes and Fluorescence Properties of the Products

A general and effective palladium-catalyzed cross-coupling of organostibines with styrenes to give (E)-olefins was disclosed. By the use of an organostibine reagent, this method can produce unsymmetric (E)-1,2-diarylethylenes and (1E,3E)-1,4-diarylbuta-1,3-dienes in good yields with high E/Z selectivity and good functional group tolerance. Resveratrol and DMU-212 were synthesized in high yield. The protocol can be extended to the synthesis of (1E,3E,5E)-1,6-diphenylhexa-1,3,5-triene in 40% yield. Products 5e, 5f, and 7a showed good photoluminescence quantum yields ranging from 72 to 99%.

Build-up of double carbohelicenes using nitroarenes: Dual role of the nitro functionality as an activating and leaving group

The construction of double carbohelicenes is highly fascinating yet challenging work. Disclosed herein is a streamlined and simplified synthetic route to double carbohelicenes starting from nitroarenes through sequential nitro-activated ortho-C-H arylation, denitrative alkenylation and intramolecular cyclodehydrogenation. In this synthetic strategy, the nitro group plays a dual role namely as a leaving group for the denitrative alkenylation and as an activating group for ortho-C-H arylation, which is distinct from those of aryl halides in a conventional coupling reaction. In this work, the palladium-catalyzed Heck-type alkenylation of nitroarenes has been presented, in which the conventionally inert Ar-NO2 bond is cleaved. This work provides a novel synthetic strategy for polycyclic aromatic hydrocarbons (PAHs). This journal is

Mizoroki-Heck Cross-Coupling of Bromobenzenes with Styrenes: Another Example of Pd-Catalyzed Cross-Coupling with Potential Safety Hazards

The potential safety hazards associated with the Mizoroki-Heck cross-coupling of bromobenzenes with styrenes were evaluated. The heat output from the reaction in various solvents was comparable in a variety of solvents; however, the rate of reaction was significantly faster in the presence of water. Thermal stability evaluation of the postreaction mixtures in DMSO and 3:1 DMSO/water by differential scanning calorimetry indicated that the onset temperatures of thermal decomposition were significantly lower than that of neat DMSO. Evaluation of the substrate scope revealed that the substitution pattern on the bromobenzene did not affect the heat output. The reaction rate of electron-deficient bromobenzenes was slower than that of the electron-rich bromobenzenes. In general, substituted styrenes afforded similar magnitudes of exotherms; however, the reaction rate of bromobenzene with 2-methylstyrene was significantly slower than the other studied styrenes. The predicted heat of reaction using the density functional theory method, B3LYP, was in good agreement with the experimental data. Such excellent agreement suggests that this calculation method can be used as a preliminary tool to predict heat of reaction and avoid exothermic reaction conditions. In many of the studied cases, the maximum temperature of a synthesis reaction was considerably higher than the solvent boiling point and thermal decomposition onset temperatures when the reaction was performed in DMSO or 3:1 DMSO/water. It is crucial to understand the thermal stability of the reaction mixture to design the process accordingly and ensure the reaction temperature is maintained below the onset temperature of decomposition to avoid potential runaway reactions.

Decarboxylative Arylation of α,β-Unsaturated Carboxylic Acids Using Aryl Triazenes by Copper/Ionic Liquid Combination in PEG-400

A practical method for the construction of stilbene derivatives has been developed via catalytic cross-coupling of cinnamic acids with aryl triazenes. The methodology offers high stereoselectivity and is endowed with broad substrate scope, high yield, and significant functional group tolerance.

Stereodivergent Alkyne Reduction by using Water as the Hydrogen Source

A homogeneous Pd-catalyzed stereodivergent reduction of alkynes to Z and E alkenes by using H2O as the H2 source is presented. Mediated by a diboron reagent, the transfer hydrogenation has been accomplished to yield the desired geometrical isomer by rational ligand selection. The switchable stereoselectivity achieved using simple phosphine ligands is generally excellent. D2O has also been used as a D2 source for synthesizing the corresponding deuterated olefins. Supported by a gram-scale synthesis, the reaction can easily be scaled up making it an efficient way to prepare alkenes commercially as well. Mechanistic studies suggest formation of H?PdL2?OAc as the crucial step leading to the presence of two pathways involving H?Pd?B(OR)2 and molecular H2 as active intermediates.

Isolable C@Fe3O4 nanospheres supported cubical Pd nanoparticles as reusable catalysts for Stille and Mizoroki-Heck coupling reactions

Cubical Pd nanoparticles incorporated magnetic nanospheres (Pd cNPs/C@Fe3O4) are found to be efficient catalysts for Stille and Mizoroki-Heck coupling reactions. A variety of aryl halides, including chlorides, are converted to biaryls and diphenylethenes with excellent yield and high TON. This immobilization of Pd cNPs on the surface C@Fe3O4 results in structurally stable catalytic sites. The observed enhanced catalytic activity is attributed to the high density of low-coordinated Pd {1?0?0} atoms present at the surface of the Pd cNPs/C@Fe3O4 catalyst. The advantages of the proposed catalytic system are its heterogeneity, high stability, absence of any toxic ligands, gram scale applicability, magnetic separability and consequent reusability.

THERAPEUTIC AGENTS FOR SKIN DISEASES AND CONDITIONS

The present invention relates to method(s) of treating a subject afflicted with a skin disease or condition, the method comprising administering to the subject or patient in need a composition comprising a therapeutically effective amount of a substituted cis or trans- stilbene or a stilbene hybrid. A method of treating or reducing the likelihood of a skin disease or condition in a patient is an additional embodiment of the present invention. Preferred pharmaceutical compositions of the invention include nanoemulsions comprising a therapeutically effective amount of a substituted cis or trans-stilbene or stilbene hybrid and at least one antibiotic.

Selective arylation and vinylation at the α position of vinylarenes

In intermolecular Heck reactions of styrene and vinylarenes, the aryl and vinyl groups routinely insert at the β position. However, selective insertion at the α position has been very rare. Herein, we provide a missing piece in the palette of Heck reaction, which gave >20:1 α selectivity. The key to our success is a new ferrocene 1,1′-bisphosphane (dnpf) that carries 1-naphthyl groups. Our mechanistic studies revealed that the high α selectivity is partly attributable to the steric effect of dnpf. The rigid and bulky 1-naphthyl groups of dnpf sterically disfavor β insertion. What the Heck! In intermolecular Heck reactions, insertion at the β position of aromatic olefins is very common, but reversal of the selectivity for selective α insertion has been a longstanding problem. A general method to couple aryl and vinyl triflates with aromatic olefins in >20:1 α selectivity is presented. The key to this successful approach is a new ferrocene bisphosphane with naphthyl groups on the phosphorus atom (see scheme; OTf=triflate). Copyright

The aminocyclodextrin/Pd(OAc)2 complex as an efficient catalyst for the Mizoroki-Heck cross-coupling reaction

An aminocyclodextrin/Pd(OAc)2 complex is used as an efficient, reusable catalyst in the Mizoroki-Heck reaction of aryl halides/triflates with olefins to give carbon-carbon-coupled products in good to excellent yields. This simple, efficient catalytic system is applicable to a wide range of aryl and heteroaryl halides/triflates and olefins. This environmentally benign procedure is less hazardous, milder, uses a catalytic amount of ligand and Pd(OAc) 2, avoids an inert atmosphere, and catalyst recovery and reusability are achieved. Copyright